Flame-resistant polymer compositions

ABSTRACT

Flameproofing of aromatic polymers is achieved by adding a synergistic combination of (a) a phosphorus compound and (b) a compound of formula R(CH 2  X) n , wherein R is an aromatic or heterocyclic residue, X is a leaving group and n is at least 2. Preferred phosphorus compounds are esters of phosphoric acid. The flameproofed polymers may contain aromatic groups in the main chain or as side-groups, for instance styrene polymers and copolymers, aromatic polyesters, polycarbonates and polyphenylene oxides.

The present invention relates to fire retardant compositions containinga significant amount of an aromatic polymer, including linear andcrosslinked polymers, wherein the aromatic groups may be part of thepolymer chain or may be side groups.

Traditionally such aromatic polymers are made flame retardant by addingto them flame retardants containing phosphorus, halogen, antimony or anycombination of these. For example, chlorinated paraffins, chlorinatedparaffin/antimony oxide mixtures and tris(2,3-dibromopropyl) phosphatehave been used. Surprisingly, we have found that the fire retardanteffect in such polymers of phosphorus compounds, in particular certainesters of phosphorus acids can be greatly improved by the use of certainsupplemental additives. As a result, either a greater fire resistancecan be achieved without increasing the phosphorus content of the polymeror the same fire resistance can be achieved with a lower phosphoruscontent.

Accordingly, the present invention provides compositions from a polymercontaining aromatic groups in the polymer chain or as side groups, and aflame-retardant combination consisting of

(a) a phosphorus compound

(b) a compound of formula I

    r(ch.sub.2 x).sub.n                                        I

in which R represents an aromatic hydrocarbon or heterocyclic residue, nis an integer of at least 2, and each X is the same or different andrepresents a leaving group.

In the compound of formula I, each aromatic or heterocyclic ring maybear from 0 to 6 --CH₂ X groups, preferably 1-3 and most preferably 1,provided that there are at least 2 --CH₂ X groups per molecule.

Thus n may be from 2 to 12, preferably from 2 to 6 and, most preferably,from 2 to 4.

The aromatic nucleus preferably has a free ortho position next to the--CH₂ X group and the CH₂ X group is preferably positioned so as not toallow intra-molecular cyclisation.

Leaving group X in formula I is halogen, --OH, --SH, --NH₂, --CO₂ H,--PO₃ H₂, OB(OH)₂ and their derivatives, for example --OR¹, --SR¹,--NHR¹, --NR¹ R², --OB(OR¹)(OR²). Non-limiting examples of suchderivatives and other X groups may be represented by the generalformulae --Y--C(W)--Z, --Y--P(L)(Y¹ R¹)(Y² R²) or --Y--SO(M)--Z

where

Y,y¹ and Y² are, independently, --O--, --NH--, --N(R¹)--, --S--, or areabsent, but preferably are --O-- or --S--

Z is H, R¹, OR¹, --SR¹, NH₂, NHR¹, NR¹ R² or a direct bond linking C(W)back to R or to a CH₂ attached to R but preferably is H or R¹ ;

W is O, S, NH or NR¹, but preferably is O or S;

L is O, S or is absent, but preferably is O;

M is O or is absent, but preferably is O;

and wherein R¹ represents a straight or branched chain alkyl having 1 to12 carbon atoms, preferably 1 to 4, but most preferably 1, alkenyl oralkynyl having 2 to 12 carbon atoms, preferably 2 to 4, cycloalkyl orcycloalkenyl having 5 to 12, preferably 6 carbon atoms, aralkyl,aralkenyl or alkaryl having 7 to 12 carbon atoms, preferably benzyl ornaphthyl methyl or aryl having 6 to 15, preferably 6 to 12 carbon atoms,most preferably benzyl or naphthylmethyl. R¹ may be optionallysubstituted by one or more halogen, hydroxy, epoxy, nitrile, amine,amide, ether, carboxyl or ester groups or combinations thereof, but ispreferably unsubstituted. R² has the same significance as R¹ and may bethe same or different. The leaving group may also be a salt of an acidicor basic X group.

However compounds of formula I where X=OH or a derivative of this groupare preferred.

The aromatic residues R may be mono- , di-, or poly-cyclic and these maybe condensed or non-condensed. The non-condensed, di and poly-cyclicaromatic residues may be linked directly or through groups containingcarbon or hetero atoms or groups containing combinations of carbon andhetero atoms. The compound of formula I may, therefore, be an oligomercontaining the above mentioned aromatic hydrocarbon and heterocylicresidues formed by addition or condensation reactions.

Apart from the groups --CH₂ X and the mentioned linking groups the groupR may be otherwise unsubstituted or it may be substituted by one or morehalogen atoms or alkyl groups having 1 to 12 carbon atoms, preferably 1to 4, cycloalkyl groups having 5 to 12 carbon atoms, hydroxyl groups,alkoxy groups having 1 to 12, preferably 1 to 4, carbon atoms which maycontain an epoxide group, cycloalkoxy groups having 5 to 12 carbonatoms, aralkyloxy groups having 7 to 12 carbon atoms, acyloxy groupshaving 1 to 12, preferably 1 to 4, carbon atoms, carboxyl groups orcarboalkoxy groups having 2 to 12, preferably 2 to 4, carbon atoms ormixtures thereof. However, R is preferably an otherwise unsubstituted oralkyl substituted di-, tri-, or tetracyclic residue.

In formula I non-limiting examples of residue R include those derivedfrom the following systems:

where R is monocyclic

1 benzene

2 toluene

3 xylenes

4 ethyl benzene

5 mesitylene

6 durene

7 isodurene

8 ψ-cumene or cumene

9 anisole

10 phenyl acetate

11 chlorobenzene

12 bromobenzene

13 pyridine

14 triazine

15 pyrimidine

16 pyrazine

17 p-t-butyl phenol

Preferably R is derived from residues 1-10 and 17.

where R is non-condensed bicyclic

1 biphenyl

2 diphenylmethane

3 1:1-diphenylethane

4 1:2-diphenylethane

5 2:2-diphenylpropane

6 diphenylcarbinol

7 benzophenone

8 phenyl benzoate

9 diphenylacetic acid (and its esters)

10 diphenylether

11 diphenylacetonitrile

12 diphenylsulphide

13 diphenyldisulphide

14 diphenylsulphoxide

15 diphenylsulphone

16 diphenylamine

17 N,N-diphenylmethylamine

18 diphenyl methyl phosphine

19 diphenyl methyl phosphine oxide

20 diphenyl octyl phosphate

21 dipyridyl

22 3,3'-dimethyl biphenyl

23 2,2'-dimethyl biphenyl

24 4,4'-dimethyl biphenyl

25 2,2'-diphenyl dicarboxylic acid

26 stilbene

27 benzoin

28 benzil

29 benzilic acid

30 dibenzyl sulphate

31 dibenzyl oxalate

32 dibenzyl succinate

33 diphenyl carbonate

34 octyl di-styryl phosphinate

35 ferrocene

36 diphenyl succinate

37 1,2-diphenoxy ethane

Of these we prefer residues derived from Nos. 1, 2, 10 and 15.

where R is condensed bicyclic

1 naphthalene

2 methyl naphthalene

3 methoxy naphthalene

4 tetralin

5 quinoline

6 isoquinoline

7 quinoxaline

8 quinazoline

9 phthalazine

10 phthalimide

11 indole

12 benzofuran

13 benzimidazole

14 benzothiazole

15 benzotriazole

Of these we prefer naphthalene and methyl naphthalene.

where R is non-condensed tricyclic

1 terphenyl

2 triphenyl methane

3 dibenzyl benzene

4 O,O¹ -diphenyl hydroquinone

5 O,O¹ -diphenyl resorcinol

6 triphenylamine

7 triphenyl phosphine

8 triphenyl phosphine oxide

9 triphenyl phosphate

10 tricresyl phosphate

11 trixylyl phosphate

12 isopropyl phenyl/phenyl phosphates, e.g. phosphates fromisopropylated phenol sold under the trade names Reofos 30, 60 and 95.

13 triphenyl antimony

14 tribenzyl phosphate

15 diphenyl styryl phosphonate

16 triphenyl orthoformate

Of these we prefer residues derived from Nos. 1, 2, 3, 5, 6, 8, 9, 10,11 and 12.

where R is condensed tricyclic

1 anthracene

2 phenanthrene

3 phenyl naphthalene

4 acenaphthene

5 acenaphthylene

6 dihydroanthracene

7 anthrene

8 xanthene

9 xanthone

10 fluorene

11 fluorenone

12 acridine

13 phenanthridine

14 phenazine

15 benzocinnoline

16 carbazole

17 dibenzofuran

18 dibenzothiophene

19 phenothiazine

20 phenoxazine

21 α-methylstyrene dimer

22 styrene dimer

23 biphenylene

24 1-methylanthracene

Of these we prefer residues derived from Nos. 1, 2, 3, 4, 5, 10, 16, 17,21, 22 and 24.

where R is non-condensed tetracyclic

1 quaterphenyl

2 tetraphenylmethane

3 triphenyl benzene

4 2,4,6-triphenyl triazine

5 N,N¹ N¹¹ -triphenyl melamine

6 N,N¹ N¹¹ -triphenyl isocyanuric acid

7 tetraphenyl tin

8 tetraphenyl lead

9 tetraphenyl ethane

10 tetrabenzyl orthosilicate

11 2,4,6 triphenoxy triazine

12 tetraphenyl silicate

Of these we prefer residues derived from Nos. 2, 4, 5, 6 and 11.

where R is condensed tetracyclic

1 dinaphthyl

2 phenyl anthracene

3 phenyl phenanthrene

4 N-phenyl acridone

5 N-phenyl carbazole

6 N-phenyl phenothiazine

7 N-phenyl phenoxazine

8 9-phenyl acridine

9 2:3-diphenyl quinoxaline

10 triphenylene

11 aceanthrene

12 pyrene

13 naphthacene

14 fluoranthene

15 chrysene

16 dinaphthyl methane

Of these we prefer residues derived from dinaphthyl and N-phenylcarbazole.

where R is polycyclic higher than tetracyclic

1 9,10-diphenyl anthracene

2 sexiphenyl

3 rubrene

4 9,9-diphenyl xanthene

5 9,9-diphenyl acridane

6 hexacene

7 hexaphene

8 pyranthrene

In formula I non limiting examples of group X are:

chloro, bromo, hydroxyl, methoxy, ethoxy, butyloxy, cycloalkyloxy,benzyloxy, phenoxy, formyloxy, acetyloxy, benzoyloxy,

carbamoyloxy, N-methylcarbamoyloxy, N,N-dimethylcarbamoyloxy,

N-methylthiocarbamoyloxy, N,N-dimethylthiocarbamoyloxy,N-phenylcarbamoyloxy,

N-phenylthiocarbamoyloxy, methylthio,

acetylthio, thioacetylthio,

methylamino, dimethylamino, acetylamino.

Non-limiting examples of particular compounds of structure I are

where R is monocyclic

1,4-bis hydroxymethyl benzene

1,4-bis methoxymethyl benzene

1,4-bis benzoxymethyl benzene

1,4-bis chloromethyl benzene

1,4-bis acetyloxymethyl benzene

2,4,6-tris chloromethyl mesitylene

3,6-bis methoxymethyl durene

2,4,6-tris acetoxymethyl phenol

2,6-bis hydroxymethylpyridine

2,6-bis hydroxymethyl-4-t-butylphenol

1,3,5-tris hydroxymethyl benzene

1,4-bis hydroxymethyl-2,3,5,6 tetrachlorobenzene

where R is non-condensed bicyclic

4,4¹ -bis(chloromethyl)biphenyl

4,4¹ -bis(bromomethyl)biphenyl

4,4¹ (hydroxymethyl)biphenyl

4,4¹ -bis(methoxymethyl)biphenyl

4,4¹ -bis(phenyloxymethyl)biphenyl

4,4¹ -bis(benzyloxymethyl)biphenyl

4,4¹ -bis(acetyloxymethyl)biphenyl

4,4¹ -bis(formyloxymethyl)biphenyl

4-hydroxymethyl-4¹ -methoxymethyl biphenyl

4-hydroxymethyl-4¹ -acetoxymethyl biphenyl

4,4¹ -bis(dimethylaminomethyl)biphenyl

4,4¹ -bis(methylcarbamoyloxymethyl)biphenyl

2,4-bis(acetoxymethyl)-6-phenyl-phenol acetate

4,4¹ -bis(hydroxymethyl)diphenyl methane

4,4¹ -bis(methoxymethyl)diphenyl methane

4,4¹ -bis(benzyloxymethyl)diphenyl methane

4,4¹ -bis(formyloxymethyl)diphenyl methane

4,4¹ -bis(carbamoyloxymethyl)diphenyl methane3,3'-bis-(acetoxymethyl)-4,4'-bis-acetoxy-diphenylmethane

4,4¹ -bis(hydroxymethyl)benzophenone

4,4¹ -bis(hydroxymethyl)diphenyl ether

4,4¹ -bis(methoxymethyl)diphenyl ether

4,4¹ -bis(acetyloxymethyl)diphenyl ether

4,4¹ -bis(hydroxymethyl)diphenyl sulphone

3,3'-bis-(acetoxymethyl)-4,4'-bis-acetoxy-di-phenylsulphone

N,n-bis(4-hydroxymethyl phenyl)methylamine

bis(4-hydroxymethyl phenyl)octyl phosphate

4,4¹ -bis(methoxymethyl)-3,3¹ -dimethyl diphenyl

2,2-bis-(3'acetoxymethyl-4'-acetoxy-phenyl)-propane

bis-(3-(o-hydroxymethylphenoxy)-2-hydroxypropyl) ether of

1,4-butanediol

where R is condensed bicyclic

1,4-bis(chloromethyl)naphthalene

1,4-bis(hydroxymethyl)naphthalene

1,4-bis(methoxymethyl)naphthalene

1,5-bis(chloromethyl)naphthalene

1,5-bis(hydroxymethyl)naphthalene

1,5-bis(methoxymethyl)naphthalene

1,5-bis(formyloxymethyl)naphthalene

1-methyl-bis-(chloromethyl)naphthalene

2-methyl-bis-(chloromethyl)naphthalene

1-methyl-bis-(hydroxymethyl)naphthalene

2-methyl-bis-(hydroxymethyl)naphthalene

1-methyl-bis(methoxymethyl)naphthalene

2-methyl-bis(methoxymethyl)naphthalene

5,8-bis(chloromethyl)tetralin

5,8-bis(hydroxymethyl)tetralin

5,8-bis(methoxymethyl)tetralin

4,8-bis(chloromethyl)quinoline

5,8-bis(hydroxymethyl)quinoline

4,8-bis(methoxymethyl)quinoline

4,8-bis(hydroxymethyl)isoquinoline

4,8-bis(acetoxymethyl)isoquinoline

5,8-bis(chloromethyl)quinoxaline

5,8-bis(hydroxymethyl)quinoxaline

5,8-bis(formyloxymethyl)quinoxaline

5,8-bis(chloromethyl)phthalazine

3,6-bis(chloromethyl)phthalimide

4,7-bis(hydroxymethyl)indole

4,7-bis(methoxymethyl)indole

4,7-bis(hydroxymethyl)benzofuran

4,7-bis(methoxymethyl)benzofuran

4,7-bis(chloromethyl)benzofuran

4,7-bis(hydroxymethyl)benzotriazole

4,7(formyloxymethyl)benzotriazole

where R is non-condensed tricyclic

1,4-di(p-chloromethyl phenyl)benzene

1,4-di(p-hydroxymethyl phenyl)benzene

1,4-di(p-formyloxymethyl phenyl)benzene

tri(p-methoxymethyl phenyl)methane

tri(p-hydroxymethyl phenyl)methane

tri(p-chloromethyl phenyl)methane

1,4-di(p-methoxymethyl benzyl)benzene

1,4-di(p-hydroxymethyl benzyl)benzene

1,4-di(p-formyloxymethyl benzyl)benzene

1,4-di(p-chloromethyl benzyl)benzene

1,4-di(p-acetoxymethyl benzyl)benzene

0,0¹ di(p-chloromethyl phenyl)hydroquinone

0,0¹ di(p-methoxymethyl phenyl)hydroquinone

0,0¹ di(p-benzoyloxymethyl phenyl)hydroquinone

0,0¹ di(p-dimethyl aminomethyl phenyl)resorcinol

tri(p-hydroxymethyl phenyl)amine

tri(p-methoxymethyl phenyl)amine

tri(p-formyloxymethyl phenyl)phosphine

tri(p-benzoyloxymethyl phenyl)phosphine

tri(p-carbamoyloxymethyl phenyl)phosphine

tri(p-dimethylaminomethyl phenyl)phosphine oxide

tri(p-bromomethyl phenyl)phosphine oxide

tri(p-benzoyloxymethyl phenyl)phosphine oxide

tri(p-chloromethyl phenyl)phosphate

tri(p-methoxymethyl phenyl)phosphate

di(p-hydroxymethyl phenyl)mono(p-methoxymethyl phenyl)phosphate

tri(p-methoxymethyl-meta-cresyl)phosphate

mono-phenyl di(p-methoxymethyl phenyl)phosphate

mono-phenyl, mono(p-hydroxymethyl phenyl), mono(p-methoxymethyl

phenyl)phosphate

di(methoxymethyl phenyl), mono(o-isopropyl phenyl)phosphate

di(hydroxymethyl phenyl), mono(p-isopropyl phenyl)phosphate

tris (2,4-dibutoxymethyl-6-phenyl-phenyl) borate

where R is condensed tricyclic

1,4-di-hydroxymethyl anthracene

5-hydroxymethyl-1,4-di(methoxymethyl)anthracene

1,4-di-(hydroxymethyl)-5,8-di(methoxymethyl)anthracene

2,7-di(acetoxymethyl)anthracene

1,4,7-tris(acetoxymethyl)acenaphthylene

1,4,7-tris(dimethylaminomethyl)acenaphthylene

1,4,5,8-tetra(hydroxymethyl)fluorene

1,4,5,8-tetra(acetoxymethyl)xanthene

1,4,5-tri(bromomethyl)xanthene

1,4,5,8-tetra(dimethylaminomethyl)carbazole

1,4,5,8-tetra(carbamoyloxymethyl)acridine

1,4,6,9-tetra(benzoyloxymethyl)phenazine

2,7,10-tris(chloromethyl)phenanthridine

1,4,6,9-tetra(methoxymethyl)phenoxazine

1,4,6,9-tetra(hydroxymethyl)phenothiazine

1,3,3-tri-methyl-1-phenyl-4,7-di(methoxymethyl)indane

where R is non-condensed tetracyclic

tetra(3,5-di-hydroxymethyl phenyl)methane

tetra(4-methoxymethyl phenyl)methane

tetra(4-formyloxymethyl phenyl)methane

tetra(4-dimethylaminomethyl phenyl)methane

1,3,5-tri(3,5-di-chloromethyl phenyl)benzene

1,3,5-tri(4-methoxymethyl phenyl)benzene

1,3,5-tri(4-carbamoyloxymethyl phenyl)benzene

1,3,5-tri(4-benzoyloxymethyl phenyl)benzene

N,n¹,n¹¹ -tri(3,5-di-hydroxymethyl phenyl)melamine

N,n¹, n¹¹ -tri(3,5-di-formyloxymethyl phenyl)melamine

N,n¹, n¹¹ -tri(4-methoxymethyl phenyl)melamine

2,4,6-tri(3,5-di-chloromethyl phenyl)triazine

2,4,6-tri(3,5-di-carbamoyloxymethyl phenyl)triazine

2,4,6-tri(4-acetoxymethyl phenyl)triazine

N,n¹,n¹¹ -tri(3,5-dihydroxymethyl phenyl)isocyanurate

tetra(3,5-diformyloxymethyl phenyl)tin

tetra(4-hydroxymethyl phenyl)tin

tetra(4-chloromethyl phenyl)tin

tetra(4-acetoxymethyl phenyl)lead

tetra(4-bromoethyl phenyl)lead

tetra(4-methoxymethyl phenyl)lead

tetrakis-(2-butoxymethyl-phenyl)silicate

where R is condensed tetracyclic

2-phenyl-5,8-di-bromomethyl anthracene

2-phenyl-5,8-di-hydroxymethyl anthracene

2-phenyl-5,8-di-formyloxymethyl anthracene

3-phenyl-3,6-dimethoxymethyl phenanthrene

3-phenyl-3,6-di-acetoxymethyl phenanthrene

3-phenyl-3,6-di-hydroxymethyl phenanthrene

N-phenyl-2,6-di-chloromethyl carbazole

N-phenyl-2,6-di-carbamoyloxymethyl carbazole

N-phenyl-2,7-di-methoxymethyl phenothiazine

N-phenyl-2,4,6-tri-bromomethyl phenothiazine

N-phenyl-2,4,6-tri-acetoxymethyl phenoxazine

2,3-diphenyl-5,8-di-formyloxymethyl quinoxaline

2,3-diphenyl-5,8-di-hydroxymethyl quinoxaline

where R is polycyclic higher than tetracyclic

2,6-di-methoxymethyl-9,10-diphenyl anthracene

2,8-di-chloromethyl rubrene

2,6-di-hydroxymethyl-9,9-diphenyl xanthene

2,6-di-acetoxymethyl-9,9-diphenyl xanthene

2,6-di-carbamoyloxymethyl-9,9-diphenyl xanthene

1,4,6,9,12,15-hexa-methoxymethyl hexacene

poly (4,4'-dibenzyl)phthalate

poly ethylenedioxy (4,4'-dibenzyl)

When the compounds of formula I are oligomers, they have the generalformula:

    (A).sub.a (--CH.sub.2 -).sub.b [--CH.sub.2 (OCH.sub.2).sub.m OCH.sub.2 --].sub.c (--CH.sub.2 X).sub.d                            II

wherein A is at least one aromatic hydrocarbon or heterocyclic residue,X is as defined above, a is 2 to 20 but equals b+c+1, b is 0 to 19, c is0 to 19, d is 0 to 2a and m is 0 to 10, preferably 0-5, most preferably0, there being at least two of the groups (CH₂ X) and (--CH₂ OCH₂ --)per molecule.

It should be noted that the values of a, b, c, d and n are averagevalues for the average molecule of formula II.

Example of aromatic residues A are those derived from benzene,naphthalene, furan, anthracene, biphenyl and diphenyl ether. Thearomatic residue A may be unsubstituted or substituted by one or twosubstituents. It is preferably unsubstituted, but if it is substitutedit preferably carries only one substituent. Suitable substituentsinclude halogen, alkyl groups with 1 to 4 carbon atoms, haloalkyl groupswith 2 to 4 carbon atoms, hydroxyl, alkoxy with 1 to 4 carbon atoms oracyloxy with 2 to 4 carbon atoms.

The compounds represented by formula II are mixtures of oligomers with arange of molecular weights. The residues A are linked by (--CH₂ --) or[--CH₂ (OCH₂)_(m) OCH₂ --] groups, these two linking groups beingconnected only to a residue A and not to each other. The groups (--CH₂X) are connected to a residue A.

Preferably more than 50 mol % of residues A are derived fromnaphthalene; most preferably more than 75 mol % of residues A arederived from naphthalene.

Oligomers which are preferred are those having a number average weightof 300 to 3500, more preferably those having a number average molecularweight of 350-1500, most preferably 400 to 1000. It is preferred thatthe naphthalene residues are linked by (--CH₂ OCH₂ --) and that theselinks should be attached to the positions 1,4; 1,5; 1,6; 1,7; 2,5; 2,6or 2,7 on the naphthalene residue. It is most preferred that the linksshould be attached to the 1,4 or 1,5 positions on the naphthaleneresidue.

Non-limiting examples of particular oligomers of structure II are thoselinked by the group --CH₂ OCH₂ -- and having two or more --CH₂ X groupsper molecule. Preferred structures which can be present as a componentof the oligomer mixture are shown by the following formulae: ##STR1##where X is --OH, --OCOCH₃, --OCH₂ C₆ H₅ or --OC₆ H₅.

Specific Examples of oligomers which can be present as components of theoligomer mixture are listed in Table A ##STR2##

                                      Table A                                     __________________________________________________________________________    No.                                                                              a  b c  m d R.sup.4                                                                            R.sup.1                                                                          R.sup.5                                                                            R                                                 __________________________________________________________________________    1  0  0 1  0 2 --   -- --   --CH.sub.2 OH                                     2  1  1 1  0 2 --   -- --   --CH.sub.2 OCH.sub.3                              3  2  1 2  0 2 --CH.sub.3                                                                         -- CH.sub.3                                                                           --CH.sub.2 OH                                     4  3  2 2  0 2 --CH.sub.2 Br                                                                      -- --CH.sub.2 Br                                                                      --CH.sub.2 OH                                     5  4  1 4  0 2 --CH.sub.3                                                                         -- CH.sub.3                                                                           --CH.sub.2 OCH.sub.3                              6  5  1 5  0 2 --   -- --   --CH.sub.2 OC(O)CH.sub.3                          7  6  2 5  3 2 --   -- --   --CH.sub.2 OH                                     8  7  2 6  0 2 CH.sub.3                                                                           CH.sub.3                                                                         CH.sub.3                                                                           --CH.sub.2 OC(O)CH.sub.3                          9  8  1 8  0 2 --   -- --   --CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5              10 9  2 8  0 2 CH.sub.3                                                                           CH.sub.3                                                                         CH.sub.3                                                                           --CH.sub.2 OC.sub.6 H.sub.5                       11 10 4 7  5 2 --   -- --   --CH.sub.2 OH                                     12 11 5 7  0 2 Br   Br Br   --CH.sub.2 Br                                     13 12 3 10 0 2 --   -- --   --CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5              14 13 4 10 0 2 CH.sub.3                                                                           CH.sub.3                                                                         CH.sub.3                                                                           --CH.sub.2 OC(O)CH.sub.3                          15 14 3 12 0 2 --   -- --   --CH.sub.2 OH                                     16 5  1 5  6 2 --   -- --   --CH.sub.2 OH                                     17 15 0 16 0 2 --   -- --   --CH.sub.2 OC(O)CH.sub.3                          18 16 0 17 0 2 --   -- --   --CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5              19 17 9 9  0 2 --   -- --   --CH.sub.2 OH                                     20 1  0 2  0 2 --   -- --   --CH.sub.2 OH                                     __________________________________________________________________________

The phosphorus compounds (a) include phosphine oxides and derivatives orsalts of phosphorus acids. The derivatives and salts of phosphorus acidsare preferred, the esters of phosphorus acids being more preferred andesters of pentavalent phosphorus, in particular phosphoric acid, aremost preferred.

The phosphorus acids include derivatives of phosphoric acid, phosphonicacid, phosphinic acid, phosphorous acid or their dehydration productsand their alkali metal, ammonium or amine salts. The acid groups inpartial esters may be present as free acid groups, but preferably astheir salts, e.g. as alkali metal or ammonium salts.

Non limiting examples of the phosphorus esters based on phosphoric acidare:

1 triphenyl phosphate

2 cresyl diphenyl phosphate

3 phenyl xylyl phosphate

4 tri-tolyl phosphate

5 tri-xylyl phosphate

6 phenyl/isopropyl phenyl phosphates (for example those sold under thetrade name Reofos 95, 65 and 50, and prepared as described in U.K. Pat.Specification No. 1,146,173).

7 phenyl/secbutyl phenyl phosphate

8 phenyl/p-t-butyl phenyl phosphate

9 di (o-cumyl phenyl) phenyl phosphate

10 di (p-benzyl phenyl) phenyl phosphate

11 tri-(p-t-butyl phenyl) phosphate

12 tri-(p-nonyl phenyl) phosphate

13 tri-(p-t-amyl phenyl) phosphate

14 tri-(p-chlorophenyl) phosphate

15 tri-[o-(bromo isopropyl) phenyl] phosphate

16 tri-[p-(bromo isopropyl) phenyl] phosphate

17 diphenyl hydrogen phosphate

18 di(o-isopropylphenyl) hydrogen phosphate

19 phenyl di-hydrogen phosphate di-sodium salt

20 diphenyl hydrogen phosphate sodium salt

21 diphenyl 2-bromoethyl phosphate

22 diphenyl 2-chloroethyl phosphate

23 diphenyl 2,3-dibromopropyl phosphate

24 diphenyl 2,3-dichloropropyl phosphate

25 diphenyl n-octyl phosphate

26 diphenyl n-decyl phosphate

27 phenyl n-octyl hydrogen phosphate ammonium salt

28 phenyl 2,3-dibromopropyl phosphate potassium salt

29 phenyl di-(2-bromoethyl) phosphate

30 phenyl di(2-chloroethyl) phosphate

31 phenyl di-(2,3-dichloropropyl) phosphate

32 phenyl di(2,3-dibromopropyl) phosphate

33 phenyl di-n-octyl phosphate

34 phenyl di-n-decyl phosphate

35 di-n-decyl hydrogen phosphate

36 di-(2-bromoethyl) hydrogen phosphate sodium salt

37 2,3-bromopropyl methyl hydrogen phosphate

38 tri-(2-chloroethyl) phosphate

39 tri-(2-bromoethyl) phosphate

40 tri-(2,3 dibromopropyl) phosphate

41 tri-(2,3-dichloropropyl) phosphate

42 tri-octyl phosphate

43 tri-decyl phosphate

44 tri-allyl phosphate

Non limiting examples of esters based on phosphonic acid are:

45 di-phenyl phenyl phosphonate

46 di-(p-bromophenyl) phenyl phosphonate

47 di-(p-t-butyl phenyl) phenyl phosphate

48 di-(o-isopropyl phenyl) phenyl phosphonate

49 di-(p-benzyl phenyl) phenyl phosphonate

50 diphenyl styryl phosphonate

51 diphenyl 1,2-dibrom-2-phenylethyl phosphonate

52 diphenyl n-octyl phosphonate

53 diphenyl n-decyl phosphonate

54 di-(p-chlorophenyl) n-butyl phosphonate

55 di-(p-bromophenyl) n-hexyl phosphonate

56 di-(o-isopropyl phenyl) n-octyl phosphonate

57 phenyl n-octyl n-hexyl phosphonate

58 phenyl styryl hydrogen phosphonate or its sodium salt

59 di-phenyl hydrogen phosphonate

60 phenyl n-octyl phosphonate ammonium salt

61 bis-2,3-dibromopropyl 2,3-dibromo propyl phosphonate

62 N-hydroxymethyl 2-diethylphosphonopropionamide

63 N-diethylphosphonomethyl diethanolamine

Non limiting examples of esters based on phosphinic acid are:

64 n-octyl di-styryl phosphinate

65 n-octyl di-(1,2-dibromo-2-phenyl-ethyl) phosphinate

66 phenyl di-styryl phosphinate

67 n-octyl di-styryl phosphinate

Non limiting examples of esters based on phosphorus acid are:

68 triphenyl phosphite

69 tri-octyl phosphite

70 tri(p-nonyl-phenyl)phosphite

71 tri(2:3-dibromopropyl)phosphite

72 diphenyl hydrogen phosphite

73 dioctyl hydrogen phosphite

None limiting examples of phosphine oxides are:

74 triphenyl phosphine oxide

75 tris (o-isopropylphenyl) phosphine oxide

76 tris (p-t-butyl phenyl) phosphine oxide

77 tris (p-isoproyl phenyl) phosphine oxide

78 tris (p-cresyl phenyl) phosphine oxide

79 tris (m-cresyl phenyl) phosphine oxide

Prferred compounds are the esters of pentavalent phosphorus and, moreparticularly, triaryl phosphates and trihaloalkyl phosphates, forexample compounds 1 to 10 and 38 to 41.

It should be understood that where an ester of a phosphorus acid alsohas the formula R(CH₂ X)_(n), it is regarded as being a compound of theformula I and should be used in conjunction with another ester of aphosphorus acid which does not fit the formula R(CH₂ X)_(n). Except ifanother R(CH₂ X)_(n) component is present, then the phosphorus acidester of formula R(CH₂ X)_(n) can be regarded as the ester component.

The compositions of the invention may contain the components (a) and (b)in the ratios a:b of 1:10 to 10:1, but preferably 1:1 to 8:1, and mostpreferably 2:1 to 4:1, by weight.

The amount of (a) together with (b) which can be used per hundred partsof polymer are from 1 to 100 parts, preferably 2-35 parts and, mostpreferably, 5 to 25 parts by weight. The actual amounts of (a) plus (b)used will vary depending on the particular polymer used and on the typeand amount of other ingredients which may be present such as fillers andre-inforcing fibres (described hereinafter).

The aromatic polymers may be homo-polymers, copolymers (the co-monomerbeing either aliphatic or aromatic), or polyblends with other polymers.

When the aromatic group is a side group of the polymer, the polymerpreferably is a vinylaromatic polymer and more preferably it is astyrene based polymer. Non limiting examples of these polymers arepolystyrene, poly-α-methyl styrene, polyvinyl toluenes,polychlorostyrenes or a co-polymer with other monomers. Non-limitingexamples of co-polymers are styrene/α-methyl styrene,styrene/acrylonitrile, styrene/acrylates, styrene/methacrylates,acrylonitrile/butadiene/styrene, styrene/butadiene, styrene/ethylene,styrene/propylene, styrene/butene, methylmethacrylate/butadiene/styrene, styrene/fumaric acid, styrene/itaconic,styrene/maleic esters, styrene/vinyl esters of monobasic aliphaticacids, styrene/vinyl esters of saturated monohydric alcohols,styrene/N-vinyl carbazole, styrene/acenaphthylene, styrene/sulphurdioxide, styrene/divinyl benzene.

Further examples are copolymers of styrene with unsaturated polymers,preferably polyesters. Such unsaturated polyesters usually arecopolyesters of maleic acid or other unsaturated dicarboxylic acids anda saturated dicarboxylic acid, e.g. phthalic, adipic or sebacic acidwith one or more glycols, e.g. ethylene, propylene, diethylene orbutylene glycol. On copolymerisation wih styrene a cross-linkedpolyester resin is formed. Other vinyl aromatic monomers may be usedinstead of styrene, such as α-methylstyrene or vinyl-toluene, for curingunsaturated polyesters.

Preferred vinylaromatic polymers are polystyrene itself and its blendswith a commercially available polymer, copolymers of styrene withbutadiene or butadiene/acrylonitrile (i.e. ABS) or blends of thesecopolymers with commercial polymers.

Non-limiting examples of vinylaromatic polyblends are polystyrene/PVC,polystyrene/polyphenylene oxide, styrene-acrylonitrileco-polymer/polyphenylene oxide, polystyrene/polycarbonate,polystyrene/polysulphone.

Examples of graft copolymers of styrene are styrene/nitrile rubber,styrene/isoprene rubber, styrene/ethylenepropylene copolymer orstyrene/ethylene-vinylacetate copolymer.

It should be understood that some of these polymers, e.g.styrene/butadiene can be subsequently cross-linked to form a rubberypolymer by conventional vulcanising agents such as sulphur.

If the polymer contains aromatic groups in the polymer chain, thepolymer may be a thermoplastic polymer which contains herero atoms inthe polymer chain. Non-limiting examples of such polymers arepolycarbonates, polyphenylene oxides, polysulphides, polysulphones,polysulphonates, polyamides, polyimides, polybenzimidazoles, linearpolyesters, polyhydrazides, polyanhydrides and thermoplasticpolyurethanes.

Non-limiting examples of the dihydric phenols from which polycarbonatesused in the present invention can be prepared are:

2,2 bis-(4-hydroxyphenyl)-propane; hydroquinone; resorcinol;

2,2 bis-(4-hydroxyphenyl)-pentane; 2,4' dihydroxydiphenyl methane;bis-(2-hydroxyphenyl)-methane; bis-(4-hydroxyphenyl)-methane;bis-(4-hydroxy-5-nitrophenyl)-methane; 1,1 bis-(4-hydroxyphenyl)-ethane;3,3 bis-(4-hydroxyphenyl)-pentane;

2,2' dihydroxydiphenyl, 2,6 dihydroxy naphthalene;bis-(4-hydroxyphenyl)-sulfone; 2,2' dihydroxydiphenyl sulfone;

4,4' dihydroxydiphenyl ether; and 4,4' dihydroxy-2,5-diethoxydiphenylether.

Two or more different dihydric phenols may be used if required. Thepreferred polycarbonate is based on 2,2-bis(4-hydroxyphenyl) propane.

Non-limiting examples of polycarbonate poly blends which may be used inthe present invention are the blends with a polyester (e.g. 1,4-butyleneterephthalate), polyethylene, polypropylene, polyisobutylene,co-polymers of ethylene and propylene, cellulose acetate, butyrate, orcopolymers of ethylene and alkyl acrylate. The poly blends can contain50% poly carbonate, but preferably contain at least 75% polycarbonateand most preferably at least 85% polycarbonate.

The linear polyesters of the invention can be represented by the residueresulting from (i) self-esterification of a hydroxy-acid --O--R--CO-- or(ii) condensation of a dihydroxy alcohol and a dibasic acid--O--R--O--CO--R'--CO--.

Preferred polyesters are those based on phthalic acid or anhydride,terephthalic acid or isophthalic acid and a glycol. Non-limitingexamples of polyesters are polyethylene terephthalate, poly(1,3-propylene) terephthalate and poly (1,4-butylene) terephthalate.

If required, co-polymerisation of dimethyl terephthalate and ethyleneglycol with a third component can be carried out to increase dyeaffinity. Non-limiting examples of such substances are iso-phthalicacid, p-hydroxy-benzoic acid and polyethylene glycol. These polyesterscan also be modified by replacing terephthalic acid with1,2-diphenoxyethane-4,4'-dicarboxylic acid.

Non-limiting examples of other polyesters are those based onp-hydroxybenzoic acid and ethylene oxide, p-hydroxybenzoic acid,p(2-hydroxyethyl)benzoic acid and terephthalic acid and1,4-bis-hydroxymethyl cyclohexane.

Non-limiting examples of the polyphenylene oxides which can be used inthe present invention are those derived from repeated residues of theformula: ##STR3## wherein R⁴, R⁵, R⁶ and R⁷ may be the same ordifferent, and each is a hydrogen or halogen atom, or a hydrocarbon,substituted hydrocarbon, cyano, alkoxy, phenoxy, amino, sulpho or nitrogroup. For example, R⁴, R⁵, R⁶ and R⁷ may be hydrogen, chlorine, bromineor iodine atoms, or methyl, ethyl, propyl, allyl, phenyl, benzyl,methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, methoxy,ethoxy, phenoxy or nitro groups. Specific examples of such polyphenyleneoxides include poly-2,6-dimethyl-1,4-phenylene oxide,poly-2,6-diethyl-1,4-phenylene oxide, poly-2,6-dipropyl-1,4-phenyleneoxide, poly-2,6-dimethoxy-1,4-phenylene oxide,poly-2,6-dichloro-methyl-1,4-phenylene oxide,poly-2,6-dibromomethyl-1,4-phenylene oxide,poly-2,6-diphenyl-1,4-phenylene oxide, poly-2,6-diphenyl-1,4-phenyleneoxide, poly-2,6-ditolyl-1,4-phenylene oxide,poly-2,6-dichloro-1,4-phenylene oxide andpoly-2,5-dimethyl-1,4-phenylene oxide.

The preferred polyphenylene oxide is poly-2,6-dimethyl 1,4-phenyleneoxide. Poly blends of polyphenylene oxide with other polymers can alsobe used such as blends with polystyrene.

The preferred thermoplastic polyurethanes are those based on adipicacid, 1,4-butanediol and 4,4'-diphenyl methane di-isocyanate.

The polymer may be in sheet form, be moulded or be foamed.

The invention further relates to flame resistant cross-linked orcross-linkable polymers containing aromatic groups in the polymer chain.These comprises cross-linked polyester resins not containingvinylaromatic component. Non-limiting examples are copolymers ofunsaturated polyesters containing aromatic components with tri allylcyanurate, diallyl phthalate, triallyl phosphate, methyl methacrylate,ethylenglycol diacrylate or trimethylolpropane trisacrylate. Unsaturatedpolyesters containing aromatic components are polyesters or copolyestersfrom aromatic decarboxylic acids, e.g. phthalic or isophthalic acid, orfrom aromatic diols, e.g. 2,2-bis(4-hydroxyphenyl)propane or1,2-bis(2-hydroxy ethoxy)benzene. Another type of curable aromaticpolyesters are the polyesters from phthalic acid and glycerol andpossibly other diols and other polycarboxylic acids, which are known asalkyd resins.

Non-limiting examples of mixtures of compounds (a) and (b) which may beused with the polymers are listed below:

4,4'-bis hydroxymethyl biphenyl and tris(2,3-dichloropropyl) phosphate

4,4'-bis hydroxymethyl biphenyl and tris(2-bromoethyl) phosphate

4,4'-bis chloromethyl biphenyl and Reofos 95 (*)

4,4'-bis hydroxymethyl biphenyl and Reofos 95 (*)

4,4'-bis hydroxymethyl biphenyl and tritolyl phosphate

4,4'-bis hydroxymethyl biphenyl and triphenyl phosphate

4,4'-bis hydroxymethyl biphenyl and tris(2,3-dibromopropyl) phosphate

4,4'-bis hydroxymethyl biphenyl and phenyl di-(2-bromoethyl) phosphate

4,4'-bis (hydroxymethyl) biphenyl and tris(2-chloroethyl) phosphate

4,4'-bis methoxymethyl biphenyl and Reofos 95

4,4'-bis methoxymethyl biphenyl and tri-tolyl phosphate

4,4'-bis methoxymethyl biphenyl and triphenyl phosphate

4,4'-bis methoxymethyl biphenyl and cresyl diphenyl phosphate

4,4'-bis(acetoxymethyl)biphenyl and Reofos 95

4,4'-bis(acetoxymethyl)biphenyl and cresyl diphenyl phosphate

4,4'-bis(acetoxymethyl)biphenyl and iso-decyl diphenyl phosphate

4,4'-bis(acetoxymethyl)biphenyl and tris[o-(bromo isopropyl) phenyl]phosphate

4,4'-bis(acetoxymethyl)biphenyl and tris(2,3-di-bromopropyl) phosphate

4,4'-bis(acetoxymethyl)biphenyl and phenyl di(2-bromoethyl) phosphate

1,5-bis-hydroxymethyl naphthalene and tris (2,3-dichloropropyl)phosphate

1,5-bis-hydroxymethyl naphthalene and tris (2-bromo ethyl) phosphate

1,5-bis-hydroxymethyl naphthalene and Reofos 95

1,5-bis-hydroxymethyl naphthalene and tritolyl phosphate

1,5-bis-hydroxymethyl naphthalene and triphenyl phosphate

1,5-bis-hydroxymethyl naphthalene and tris (2,3-dibromopropyl) phosphate

1,4-bis-hydroxymethyl naphthalene and phenyl di(2-bromoethyl) phosphate

1,5-bis-hydroxymethyl naphthalene and tris (2-chloroethyl) phosphate

1,5-bis-hydroxymethyl naphthalene and cresyl diphenyl phosphate

1,4-bis-methoxymethyl naphthalene and tris (2,3-dichloropropyl)phosphate

1,5-bis-methoxymethyl naphthalene and tris (2-bromoethyl) phosphate

1,5-bis-methoxymethyl napththalene and Reofos 95

1,5-bis-methoxymethyl naphthalene and tritolyl phosphate

1,5-bis-methoxymethyl naphthalene and triphenyl phosphate

1,4-bis-methoxymethyl naphthalene and tris (2,3-dibromopropyl) phosphate

1,5-bis-methoxymethyl naphthalene and phenyl di(2-bromoethyl) phosphate

1,5-bis-methoxymethyl naphthalene and tris (2-chloroethyl) phosphate

1,5-bis-methoxymethyl naphthalene and cresyl diphenyl phosphate

1,5-bis-hydroxymethyl naphthalene and triphenyl phosphine oxide

4,4'-bis-methoxymethyl biphenyl and tricresyl phosphine oxide

1,4-bis-hydroxy naphthalene and tris-(4-isopropylphenyl) phosphine oxideMixtures of phosphorus compounds can be used, if desired, as canmixtures of compounds of formula I.

Compounds of type (b) which have been found to have a particularlymarked fire retardant effect are those of the formula: ##STR4## where Xrepresents Cl, OH, OR¹ or acyloxy, and R¹ is as defined before. Thesecompounds are preferably used in admixture with aromatic phosphates orhalo-alkyl phosphates or aryl haloalkyl phosphates or mixtures thereof.Most preferred are mixtures of compounds of the above structure andaromatic phosphates.

Compounds of type (b) may optionally be mixed with other non-deactivatedaromatic compounds containing vacant positions on an aromatic ring, suchas compounds of the formula RCH₂ X where R and X are as defined above.In some cases further enhancement of fire retardance may be obtainedthereby. Non-limiting examples of such compounds are: 4-acetoxydiphenylmethane, 4-methoxy diphenyl methane, 4-acetoxy (2,2-diphenylpropane), 4-methoxy (2,2-diphenyl propane), 1-acetoxy naphthalene,1-methoxy naphthalene, 1-acetoxy-4-phenyl benzene, 1-acetoxy-2-phenylbenzene, 1-hydroxy methyl naphthalene, 1-hydroxymethyl-4-phenyl benzene,diphenyl ether, biphenyl, terphenyl, polybenzyl, Novolaks and Novolakethers, e.g. glycidyl ethers, polyphenyl ethers, 4-hydroxy methylbiphenyl, 4-hydroxy methyl diphenyl ether, 4-methoxy methyl diphenylether, 4-acetoxy methyl diphenyl ether, 1-hydroxy methyl-2-phenylbenzene, mono-methyl monohydroxymethyl naphthalenes, mono-hydroxymethylphenanthrene.

The compositions of the invention may also contain other additives usualin plastics technology. For example they may contain heat stabilisers,light stabilisers, UV absorbers, antioxidants, fillers, pigments,lubricants, additives to improve mold release, fungicides, blowingagents, optical brightening agents or other fire retardant additives.Suitable antioxidants include the sterically hindered phenol compoundsfor example: 2,2'-thio-bis-(4-methyl-6-tert.butylphenyl),4,4'-thio-bis-(3-methyl-6-tert.butylphenol),2,2'-methylene-bis(4-methyl-6-tert.butylphenyl), 2,2'-bis(4,4'-phenylol)propane, 2,2'-methylene-bis-(4-ethyl-6-tert.butylphenyl),4,4'-methylene-bis-(2-methyl-6-tert.butyl-phenol),4,4'-butylidene-bis-(3-methyl-6-tert.butylphenol),2,2'-methylene-bis[4-methyl-6-(α-methyl-cyclohexyl)-phenol],2,6-di(2-hydroxy-3-tert.butyl-5-methylbenzyl) 4-methyl-phenol,2,6-di-bert.butyl-4-methylphenol,1,1,3-tris-(2-methyl-4-hydroxy-5-tert.butyl-phenyl)-butane,1,3,5-trimethyl-2,4,6-tri(3,5-di-tert.butyl-4-hydroxy-benzyl-benzene,esters of β-4-hydroxy-3,5-di-tert.butylphenyl-propionic acid withmonohydric or polyhydric alcohols, such as methanol, ethanol,octadecanol, hexanediol, noneanediol, thiodiethylene glycol,trimethylolethane or pentaerythritol,2,4-bis-octylmercapto-6-(4-hydroxy-3,5-di-tert.butylanilino)-s-triazine,2,4-bis-(4-hydroxy-3,5-di-tert.butylphenoxy)6-octylmercapto-s-triazine,1,1-bis(4-hydroxy-2-methyl-5-tert.butylphenyl)-3-dodecylmercapto-butane, 2,6-di-t-butyl-p-cresol,2,2-methylene-bis(4-methyl-6-t-butylphenol),4-hydroxy-3,5-di-tert.butylbenzylphosphonic acid esters, such as thedimethyl, diethyl or dioctadecyl ester, (3-methyl-4-hydroxy-5-tert.butylbenzyl)-malonic acid dioctadecyl ester,s-(3,5-dimethyl-4-hydroxyphenyl)-thioglycollic acid octadecyl ester, andesters of bis-( 3,5-di-tert.butyl-4-hydroxybenzyl)-malonic acid, such asthe didodecyl ester, the dioctadecyl ester and 2-dodecylmercaptoethylester.

Suitable light stabilisers and UV absorbers include: sterically hinderedcyclic amines of the formula III ##STR5## and salts thereof in which qis 1 or 2, X represents an organic grouping which complements thenitrogen-containing ring to give a 5-membered, 6-membered or 7-memberedring, R₁ and R₂ represent methyl or together represent --(CH₂)₅ --, R₃represents methyl, R₄ represents alkyl with 1-5 carbon atoms or togetherwith R₃ represents the radicals --(CH₂)₄ --, --(CH₂)₅ --, --CH₂--C(CH₃)₂ --NH--C(CH₃)₂ --CH₂ -- or --CH₂ --C(CH₃)₂ --N(O)--C(CH₃)₂--CH₂ -- and, if q is 1, Y denotes hydrogen, --O; hydroxyl, alkyl,substituted alkyl, alkenyl, alkynyl, aralkyl, substituted aralkyl oracyl or, if q is 2, Y denotes alkylene, alkenylene, alkynylene,cycloalkylene or aralkylene.

Examples of sterically hindered cyclic amines of formula III are4-benzoyloxy-, 2,2,6,6-tetremethylpiperidine;4-capryloyloxy-2,2,6,6-tetramethylpiperidine;4-stearoyloxy-2,2,6,6-tetremethylpiperidine;bis-(2,2,6,6-tetramethyl-4-piperidyl)-sebacate;bis-(2,2,6,6-tetramethyl-4-piperidyl)-dodecanedioate andbis-(1,2,2,6,6-pentamethyl-4-piperidyl)-sebacate.

2-(2'-Hydroxyphenyl)-benztriazoles, such as for example, the 5'-methyl-,3',5'-di-tert.butyl-, 5'-tert.butyl-5'-(1,1,3,3-tetramethylbutyl)-,5-chloro-3',5'-di-tert.butyl-, 5-chloro-3'-tert.butyl-5'-methyl-,3'-sec.butyl-5'-tert.butyl-, 3'-α-methylbenzyl-5'-methyl-,3'-α-methylbenzyl-5'-methyl-5-chloro-, 4'-hydroxy-, 4'-methoxy-,4'-octoxy-, 3', 5'-di-tert.amyl-, 3'-methyl-5'-carbomethoxyethyl- and5-chloro-3',5'-tert.-amyl-derivative.

2,4-Bis-(2'-hydroxyphenyl)-6-alkyl-s-triazines, such as for example, the6-ethyl-, 6-heptadecyl- or 6-undecylderivative.

2-Hydroxy-benzophenones, such as, for example, the 4-hydroxy-,4-methoxy-, 4-octoxy-, 4-decyloxy, 4-dodecyloxy-, 4-benzyloxy-,4,2',4'-trihydroxy- or 2'-hydroxy-4,4'-dimethoxyderivative.

1,3-Bis-(2'-hydroxybenzoyl)-benzenes, such as, for example,1,3-bis-(2'-hydroxy-4'-hexyloxy-benzoyl)-benzene,1,3-bis(2'-hydroxy-4'-octyloxy-benzoyl)-benzene and1,3-bis(2'-hydroxy-4'-dodecyloxy-benzoyl)-benzene.

Esters of optionally substituted benzoic acids, such as, for example,phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol,bis-(4-tert.-butylbenzoyl)-resorcinol, benzoylresorcinol and3,5-di-tert.-butyl-4-hydroxybenzoic acid 2,4-di-tert.butyl-phenyl esteror octadecyl ester or 2-methyl-4,6-di-tert.butyl-phenyl ester.

Acrylates, such as, for examle, α-cyano-β,β-diphenylacrylic acid ethylester or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester,α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester andN-(β-carbomethoxy-vinyl)-2-methyl-indoline.

Oxalic acid diamides, such as, for example, 4,4'-di-octyloxy-oxanilide,2,2'-di-octyloxy-5,5'-di-tert.butyl-oxanilide,2,2'-di-dodecyloxy-5,5'-di-tert.butyl-oxanilide,2-ethoxy-2'-ethyl-oxanilide, N,N'-bis-(3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert.butyl-2'-ethyl-oxanilide and its mixture with2-ethoxy-2'-ethyl-5,4'-di-tert.butyl-oxanilide and mixtures of ortho-and para-methoxy- as well as of o- and p-ethoxy-disubstitutedoxanilides.

Nickel compounds, such as, for example, nickel complexes of2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine, nickel complexes ofbis-[2-hydroxy-4-(1,1,3,3-tetramethylbutyl)-phenyl]-sulphone, such asthe 2:1 complex, optionally with additional ligands such as2-ethyl-caproic acid, nickel dibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert.butylbenzyl-phosphonic acid monoalkyl esters, suchas the methyl, ethyl or butyl ester, nickel complexes of ketoximes suchas of 2-hydroxy-4-methyl-phenyl-undecylketonoxime and nickel3,5-di-tert.butyl-4-hydroxy-benzoate.

When compositions contain a halogenated compound such as PVC they maycontain conventional PVC stabilisers.

These additives may be used alone or in any combination.

The compositions may also contain other stabilising and lubricatingcomponents such as:

pentacrythritol, triphenyl phosphite, decyl diphenyl phosphite, didecylphenyl phosphite, trinonyl phenyl phosphite, stearic acid, hydroxystearic acid, low molecular weight polyethylene wax, mineral oil, butylstearate, paraffin wax, oxidised paraffin wax, fatty alcohols, esters ofstraight chain fatty alcohols and straight chain fatty acids (in whichthe acids or alcohols are natural or synthetic), monoesters of glycolsand straight chain fatty acids, methylene bis stearamide. Suitablepigments include organic and inorganic pigments or mixtures thereof. Ifan organic pigment is used it may be, for example, a phthalocyaninewhich may be a metal phthalocyanine such as copper phthalocyanine, ametal free phthalocyanine or a chlorinated metal or metal freephthalocyanine, for example a chloromethylated phthalocyanine. Otherorganic pigments include azo pigments (monoazo or diazo), anthraquinoneand metal complexes. If an inorganic pigment is used, it may be forexample, titanium dioxide, carbon black or iron oxide. Additives toimprove mould release for use with moulded compositions include longchain acids and amides. Suitable fillers include asbestos, glass fibers,kaolin and talc.

The composition may also contain blowing agents when a foamedcomposition is desired, non-limiting examples being aliphatichydrocarbons of chain length up to C₇, mixtures of sodium bicarbonate orcarbonate with acetic, fumaric, malonic, citric or tartaric acids whichproduce carbon dioxide, and N-containing blowing agents, and halogenatedhydrocarbons.

Other conventional fire retardant additives may be present, such asantimony oxide, chlorinated paraffins, or brominated alkyl or brominatedaryl derivatives.

Compounds (a) and (b) may be incorporated into the polymer in a numberof ways. For example, in the case of polystyrene, they may be added tostyrene which is then polymerised in the presence of compounds (a) and(b) or the polystyrene may be dissolved in a solvent and compounds (a)and (b) added to the solution. The polymer granules may be dry-blendedwith compounds (a) and (b) in a high speed mixer, and the dispersion fedto a compounder-extruder for meltblending, and finally granulating. Inthe case of crosslinkable polymers (a) and (b) are added before thecuring operation.

The aromatic compounds of formula I used in the present invention areeither known or can be readily prepared by well established methods. Forexample the parent aromatic compound may be chloromethylated by reactionwith formaldehyde and hydrogen chloride gas. This reaction is describedin "Organic Reactions", Vol. I, 63 (1942). Displacement of the chlorineatom by other nucleophiles can give other compounds of the presentinvention.

Examples of these reactions are: ##STR6## R.CH₂ Cl compounds may also beprepared by side-chain chlorination of methyl groups, i.e. by reactionof R.CH₃ compounds with chlorine gas.

Groups other than --CH₂ Cl may be introduced directly into an aromaticnucleus by one stage reactions. Reactions of this type are reviewed in"Formation of C-C Bonds," Vol I by Jean Mathieu and Jean Weill-Raynal.Examples of CH₂ X groups which may be directly introduced into anaromatic nucleus are:

--CH₂ OH, --CH₂ OCH₃, --CH₂ OCOCH₃, --CH₂ SC₂ H₅, --CH₂ SC₆ H₅, --CH₂N(CH₃)₂, --CH₂ N(C₂ H₅)₂,

Other, less direct, routes to R(CH₂ X)_(n) type compounds may beemployed. For example an aldehyde group can be introduced into anaromatic compound either directly by reaction with carbon monoxide or byhydrolysis of a di-alkoxymethylated or di-halomethylated aromatic. Thealdehyde group may then be reduced to a hydroxymethyl group.

The hydroxymethylated aromatic may also be used as an intermediate inthe preparation of other R(CH₂ X)_(n) compounds, for example

    R.CH.sub.2 OH+C.sub.6 H.sub.5 CH.sub.2 Cl→R.CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5

    r.ch.sub.2 oh+(ch.sub.5 co).sub.2 o→r.ch.sub.2 ococh.sub.3

    r.ch.sub.2 oh+ch.sub.3 c.sub.6 h.sub.4 so.sub.2 cl→R.CH.sub.2 OSO.sub.2 C.sub.6 H.sub.4 CH.sub.3

more detailed methods of preparation of compounds of the presentinvention are given below. These methods are exemplified here bypreperation of biphenyl derivatives but may be employed to producederivative of other aromatic R groups.

Method A. 4,4'-Bis(chloromethyl)biphenyl

0.1 mole diphenyl, 0.075 mole paraformaldehyde, 0.07 mole zinc chlorideand 50 mls cyclohexane were treated with dry hydrochloric acid gas withstirring at 55°-60° C. for 20 hours. The reaction mixture was pouredinto water and the organic material extracted with cyclohexane which wasevaporated to dryness to give 0.06 moles product=60 percent of theory.mp=137°-8° C.

Method B. 4,4'-Bis(methoxymethyl)biphenyl

0.1 moles 4,4'bis(chloromethyl)biphenyl (prepared by method A above),0.4 moles potassium hydroxide and 150 mls of methanol were refluxed for4 hours with stirring. The reaction mixture was neutralised withconcentrated hydrochloric acid and filtered. The filtrate was evaporatedto dryness at 80° C. under water pump vacuum and the residuefractionally distilled.

The fraction boiling between 154° C. and 156° C. at 0.2 mm. Hg pressurewas collected. Yield of product=0.075 moles=75 percent of theory.

mp=47°-49° C.

Method C. 4,4'-Bis(acetoxymethyl)biphenyl

0.1 moles 4,4'bis(chloromethyl)biphenyl (prepared by method A above),0.25 moles potassium acetate and 100 mls glacial acetic acid were refluxfor 17 hours with stirring. The reaction mixture was filtered and thefiltrate evaporated to dryness at 80° C. under water pump vaccum. Theresidue was recrystallised from methanol to yield 0.068 moles product=68percent of theory.

mp=86°-87° C.

Method D. 4,4'-Bis(hydroxymethyl)biphenyl

0.1 moles 4,4'bis(acetoxymethyl)biphenyl (prepared by method C above),0.4 mole sodium hydroxide as 23 percent aqueous solution and 50 mlsethanol were refluxed for 3 hours with stirring. The reaction mixturewas filtered and the precipitate washed with water and dried to yield0.08 moles product=80 percent of theory. m.p. 195°-97° C.

The oligomers described above can be prepared by conventional methods;examples of which are:

(a) the reaction of naphthalene with formaldehyde in the presence of anacid catalyst to produce oligomers with structures having predominantlymethylene (--CH₂ --) and acetal (--(CH₂ O)_(n) --CH₂ --) links with somedi-methylene ether links (--CH₂ --O--CH₂ --) or (b) by thechloromethylation of naphthalene to produce mixtures of mono, di andhigher chloromethyl naphthalenes which are then hydrolysed andoligomerised to produce oligomers having predominently di-methyleneether (--CH₂ --O--CH₂ --) and methylene (--CH₂ --) links, or (c) byreacting a chloromethylated aromatic compounds, e.g. benzylchloride,with formaldehyde or a precursor thereof, such as tri-oxymethylene, andan acid catalyst to give a chloromethylated di-aryl methane, e.g.bis-chloromethyl diphenylmethane. The latter are hydrolysed andoligomerised with aqueous sodium carbonate or are converted via theacetoxymethyl compounds into the hydroxymethyl derivatives and thenoligomerised with an acid catalyst.

Methods of preparation of the oligomers are illustrated by the followingexamples.

Method E. Preparation of Naphthalene Oligomers (Table 8, Examples 45-48)Chloromethylation

This reaction is carried out in a fume cupboard because of the possibleformation of bis-chloromethyl ether in the vapour phase.

A 5 liter 4-neck round bottom flask is fitted with a stirrer,thermometer, gas inlet tube and a reflux condenser. The off-gas from thereaction is conveyed to a scrubber in which 2 liters of water iscontinuously circulated and maintained alkaline to phenolphthalein byaddition of 46% w/w aqueous sodium hydroxide as required.

Naphthalene (4 moles) concentrated hydrochloric acid (13.8 moles),paraformaldehyde (23.2 moles) and zinc chloride catalyst (0.19 moles)are charged to the flask and heated and stirred at 90° C. for 12 hours.During this period, hydrogen chloride gas is passed into the reactionmixture and analysis showed the degree of chloromethylation to be 1.47moles-CH₂ Cl/mole naphthalene.

Hydrolysis of chloromethylated naphthalene using aqueous sodiumcarbonate

To the crude chloromethylated naphthalene from above is added sodiumcarbonate (3.09 moles) and 2429 gms. water.

The reaction mixture is stirred and heated at 100° C. for eight hours.Sodium hydroxide (1.62 moles) is then added as a 46% w/w solution andheating and stirring at 100° C. Continued for a further six hours. Themixture is allowed to cool and the aqueous phase removed by decantation.The organic phase is washed twice with water at 60° C. and finally driedby heating and stirring for three hours at 110° C. and 20 mm. mercurypressure to give a viscous oil

(Yield=81% of theory).

Oligomerisation

The hydroxymethyl naphthalene oligomer from above is heated in toluene(about 13% w/w) with 88% phosphoric acid (1% w/w) as catalyst. Thereaction is carried out in a flask fitted with a stirrer, thermometerand a water separator surmounted by a reflux condensed. The mixture isheated for 4.5 hours at 150° C. and 0.47 moles water/mole startingmaterial are removed.

The reaction mixture is allowed to cool, diluted with chloroform, washedtwice with water and the solvent removed by heating in a distillationapparatus under reduced pressure. The product is finally stripped at110° C. for three hours at 20 mm. mercury pressure to yield 84% of abrittle solid.

Average molecular weight=550.

Method F. Preparation of Naphthalene Oligomers (Table 8, Examples 51-57)Chloromethylation

Using the method previously described, naphthalene (4 moles).concentrated hydrochloric acid (13.8 moles) formaldehyde, as 37% aqueoussolution (18.9 moles) and zinc chloride (0.19 moles) are reacted at 90°C. for 22 hours with hydrogen chloride gas passed into the reactionmixture at 230 mls./minute. NMR analysis of the reaction mixture showedthe degree of chloromethylation to be 1.88 moles --CH₂ Cl/molenaphthalene.

Hydrolysis of chloromethylated naphthalene using aqueous sodiumcarbonate

To the crude chloromethylated naphthalene from above is added sodiumcarbonate (3.57 moles) and 2806 gm. water. The reaction mixture ishydrolysed as previously described with subsequent addition of sodiumhydroxide (1.35 moles) to yield 73% of a viscous liquid. Averagemolecular weight=380.

Method G. Preparation of Naphthalene Oligomers (Table 8, Example 49)Chloromethylation

Using the method previously described naphthalene (4 moles) concentratedhydrochloric acid (13.8 moles) formaldehyde as 37% aqueous solution(18.9 moles) are reacted at 90° C. for 12 hours with hydrogen chloridegas passed into the reaction mixture at 450 ml./minute. NMR analysis ofthe reaction mixture showed the degree of chloromethylation to be 1.5moles --CH₂ Cl/mole naphthalene.

Conversion of chloromethyl naphthalenes into the correspondingacetoxymethyl derivatives

To the chloromethylated naphthalene mixture from above (3.64 moles) isadded potassium acetate (9.14 moles) and glacial acetic acid (55.3moles). The reactants are stirred under reflux at 122° C. for ninehours. After cooling to room temperature the reaction mixture isfiltered and the white precipitate washed with hot acetic acid. Thefiltrate and washings are then stripped under 20 mm. mercury pressure upto a maximum internal temperature of 100° C. The residual crude productis then stirred with dichloromethane at room temperature, filtered, theprecipitate washed with dichloromethane and the combined filtrate andwashings stripped under a pressure of 20 mm. mercury up to an internaltemperature of 100° C. to leave the product an equimolar mixture of 1mono and 1,5 bis acetoxymethyl naphthalenes as the distillation residue.

Hydrolysis of acetoxymethyl naphthalenes to the correspondinghydroxymethyl naphthalenes

The acetoxymethyl naphthalene mixture from above (1.53 moles) ishydrolysed by refluxing in its own weight of ethanol with sodiumhydroxide (5.45 moles) as 20% aqueous solution for approximately 7hours. The reaction mixture is then diluted with water and cooled toroom temperature. The mixture is extracted with ether, the latter washedseveral times with water and then dried over sodium sulphate. The etheris removed by distillation and the residual product finally stripped for1 hour at 100° C. and 20 mm. mercury pressure to yield 86% of a waxysolid equimolar mixture of mono- and bis-(hydroxymethyl) naphthalenes.

Oligomers derived from hydroxymethyl naphthalenes

The mixture of hydroxymethyl naphthalenes from above is oligomerised aspreviously described by heating in toluene (about 13% w/w) with 88%phosphoric acid (1% w/w) as catalyst. The mixture is heated for 4 hoursat 150° C. and 0.53 moles water/mole starting material are removed. Theproduct is obtained in 94% yield and is a very viscous liquid, averagemolecular weight 530.

The following Examples further illustrate the invention:

EXAMPLES 1-23

Crystal polystyrene compositions were made up using several differentflame retardant compositions as set out in Table 1 and in the amountsshown (parts being by weight).

The compositions, containing 100 pts polymer, were compounded on a tworoll mill for 20-30 minutes at 120° C. The polymer was placed on themill and the flame retardant composition added portion wise over 10-20minutes. The polymer composition was then milled for a further 10-20minutes. On completion of milling the polymer was pressed into sheets 6inches by 6 inches by 0.10 inch (152×152×2,5 mm) in a press heated to120° C.

The (Limiting) Oxygen Index (OI), as described in ASTM method 2863, ofthe sheets was then measured.

In Table 1, compositions of the invention, examples 1-23 are comparedwith polystyrene formulations containing no flame retardant and priorart flame retardants.

                                      Table 1                                     __________________________________________________________________________    Flame Retardant Tests in Crystal Polystyrene                                                                       Parts                                                                Method                                                                             M. pt.                                                                            of  Phosphorus Other Oxygen                                          of   or  Cmpd.                                                                             Ester      Additive                                                                            Index               Example No.                                                                           R         X       n Prepn.                                                                             B. pt.                                                                            (I) (parts)    (parts)                                                                             %                   __________________________________________________________________________    Comparative                                                                   Example A                                                                             --        --      --                                                                              --   --  --  --         --    17.7                Comparative                              Triphenyl                            Example B                                                                             --        --                     Phosphate (20)                                                                           --    22.9                Comparative                              Tris(2-chloro-                       Example C                                                                             --        --      --                                                                              --   --  --  ethyl) phosphate                                                                         --    24.9                                                         (25)                                 Comparative                              Tris(2,3-dibromo-                    Example D                                                                             --        --      --                                                                              --   --  --  propyl)-phos-                                                                            --    28.7                                                         phate (25)                                    ##STR7## OH      2 D    m.p. 195°- 197° C.                                                  20  Triphenyl Phos- phate                                                                    --0)  30.0                2       "         "       " "    "   10  Triphenyl Phos-                                                                          --    37.1                                                         phate (25)                           3       "         "       " "    "   7.5 Triphenyl Phos-                                                                          --    31.6                                                         phate (18.5)                         4       "         "       " "    "   5   Triphenyl Phos-                                                                          --    26.5                                                         phate (20)                           5       "         "       " "    "   10  Triphenyl Phos-                                                                          --    26.2                                                         phate (15)                           6       "         "       " "    "   15  Triphenyl Phos-                                                                          --    26.1                                                         phate (10)                           7       "         "       " "    "   14  Triphenyl Phos-                                                                          --    33.7                                                         phate (35)                           8       "         "       " "    "   7.5 Triphenyl Phos-                                                                          PVC                                                                                 31.5                                                         phate (18.75)                        9       "         "       " "    "   7.5 Triphenyl Phos-                                                                          PVC                                                                                 39.4                                                         phate (18.75)                        10      "         "       " "    "   10  Tris(2,3-dibromo-                                                                        --    34.8                                                         propylphosphate)                                                              (25)                                 11      "         "       " "    "   5   Tris(2,3-dibromo-                                                                        --    33.6                                                         propylphosphate)                                                              (25)                                 12      "         "       " "    "   7.5 Triphenyl Phos-                                                                          PVC                                                                                 42.3                                                         phate (18.75)                                                                            DBTM (1)                  13                                                                                     ##STR8## "       " "        10  Tris(2,3-dibromo- propyl)phosphat                                             e (25)     --    31.2                14                                                                                     ##STR9## OCH.sub.3                                                                             " B    m.p. 50°- 52° C.                                                    10  Tris(2,3-dibromo-  propyl)phospha                                             te (25)    --    35.8                15      "         "       " "    "   10  Tris(2-chloro-                                                                           --    25.8                                                         ethyl)phosphate                                                               (25)                                 16                                                                                     ##STR10##                                                                              OH      " D        10  Triphenyl phos- phate                                                                    --5)  34.7                17                                                                                     ##STR11##                                                                              Cl      " A    m.p. 136°- 37° C.                                                   10  Tris(2-chloro- ethyl)phosphate                                                (25)       --    28.5                18      "         OH      " D    m.p.                                                                              10  Tris(trichloro-                                                                          --    26.8                                                 195°-                                                                          ethyl)phosphate                                                       97° C.                                                                         (25)                                 19      "         "       " "    "   10  Diphenyl trichlo-                                                                        --    33.8                                                         roethyl phosphate                                                             (25)                                 20      "         "       " "    "   5   Triphenyl phos-                                                                          --    31.7                                                         phate (25)                           21      "         "       " "    "   15  Triphenyl phos-                                                                          --    40.2                                                         phate (25)                           22      "                                                                                        ##STR12##                                                                            " B    m.p. 238°- 241° C.                                                  4   Tris(2-chloro- ethyl phosphate                                                (10)       --    26.1                23      "         OH      " D    m.p.                                                                              10  Tris(2-naphthyl)                                                                         --    28.8                                                 195°-                                                                          phosphate (25)                                                        97° C.                                __________________________________________________________________________     PVC = polyvinyl chloride                                                      DBTM = dibutyl tin maleate                                               

The results shown in Table 1 illustrate the great improvement in flameresistance, as measured by Oxygen Index, that is obtained by thecombined use of compounds of types a and b over polystyrene containingno FR additive and over polystyrene when it contains only a compound oftype (a).

EXAMPLES 24-27

The compositions shown in Table 2 were prepared from high impactpolystyrene according to the procedure used for Examples 1-23.

                                      Table 2                                     __________________________________________________________________________    Flame Retardant Tests in High Impact Polystyrene                                                                  Parts                                                                Method                                                                             M. pt.                                                                            of           Other                                                                              Oxygen                                             of    or Cmpd.                                                                             Phosphorus Ester                                                                       Additive                                                                           Index                   Example No.                                                                          R             X   n Prepn.                                                                             B. pt.                                                                            (I) (parts)  (parts)                                                                            %                       __________________________________________________________________________    Comparative                                                                   Example F                                                                            --            --  --                                                                              --   --  --  --       --   18.3                    Comparative                                                                   Example G                                                                            --            --  --                                                                              --   --  --  Reofos 95 (25)                                                                         --   20.3                    24                                                                                    ##STR13##    OH  2 D    M. pt. 195°- 197° C.                                                7.5 Triphenyl Phos- phate                                                                  --8.75)                                                                            31.3                    25     "             "   " "    "   10  Reofos 95 (25)                                                                         --   35.8                    26     "             Cl  2 A    M. pt                                                                             10  Reofos 95 (25)                                                                         --   26.5                                                    137° -                                                                 138° C.                                27     "             OCH.sub.3                                                                         2 B    M. pt.                                                                            10  Reofos 95 (25)                                                                         --   25.4                                                    47°-                                                                   49° C.                                 __________________________________________________________________________

the results in Table 2 clearly illustrate the marked effect of usinghigh impact polystyrene compositions containing compounds a and b over acomposition, Example F not containing compounds a and b, and ourcomposition G containing only compound (a).

EXAMPLES 28 AND 29

The compositions shown in Table 3 were prepared, according to theprocedure used for Examples 1-23, but from a copolymer of acrylonitrile,butadiene and styrene (known as ABS), and at the higher processingtemperature of 120°-140° C.

                                      Table 3                                     __________________________________________________________________________    Flame Retardant Tests in Acrylonitrile/Butadiene/Styrene-Copolymere                                               Parts                                                                Method                                                                             M. pt.                                                                            of           Other                                                                              Oxygen                                             of   or  Cmpd.                                                                             Phosphorus Ester                                                                       Additive                                                                           Index                   Example No.                                                                          R             X   n Prepn.                                                                             B. pt.                                                                            (I)   (parts)                                                                              (parts)                                                                            %                       __________________________________________________________________________    Comparative                                                                   Example H                                                                            --            --  --                                                                              --     --                                                                              --    --     --   18.2                    Comparative                                                                   Example I                                                                            --            --  --                                                                              --     --                                                                              --  Triphenyl                                                                     Phosphate (25)                                                                         --   21.0                    28                                                                                    ##STR14##    OH  2 D    M. pt. 195°- 197° C.                                                10  Triphenyl Phosphate                                                                    --5) 27.5                    29     "             OCH.sub.3                                                                         2 B    M. pt.                                                                            11.3                                                                              Triphenyl                                                                              --   25.7                                                    47°-                                                                           Phosphate (25)                                                        49° C.                                 __________________________________________________________________________

the results in Table 3 show the marked improvement in flame retardaneyby using compounds of types a and b together in a co-polymer ofpolystyrene compared with Examples H and I not containing compounds aand b.

EXAMPLES 30 AND 31

The compositions shown in Table 4 were prepared, according to theprocedure used for Examples 1-23, but with processing at 120°-130° C.from a co-polymer of styrene and acrylonitrile.

                                      Table 4                                     __________________________________________________________________________    Flame Retardant Tests in styrene/acrylonitrile-copolymer                                                            Parts                                                               Method                                                                             M. pt.                                                                             of            Other                                                                              Oxygen                                           of   or   Cmpd.                                                                             Phosphorus Ester                                                                        Additive                                                                           Index                Example No.                                                                           R              X  n Prepn.                                                                             B. pt.                                                                             (I) (parts)   (parts)                                                                            %                    __________________________________________________________________________    Comparative                                                                   Example J                                                                             --             -- --                                                                              --   --   --  --        --   19.2                 Comparative                                                                   Example K                                                                             --             -- --                                                                              --   --   --  Triphenyl --   23.6                                                           Phosphate (25)                      Comparative                                                                   Example L                                                                             --             -- --                                                                              --   --   --  Tris(2-chloro-                                                                          --   24.1                                                           ethyl)phosphate                                                               (25)                                30                                                                                     ##STR15##     OH 2 D    m. pt. 195°- 197° C.                                                 10  Triphenyl- phosphate                                                                    --5) 32.5                 31                                                                                     ##STR16##     OH 2 D    m. pt. 195°- 197° C.                                                 10  Tris(2-chloro- ethyl) phosphate                                               25)       --   31.7                 __________________________________________________________________________

The results in Table 4 show the marked improvement in flame retardaneyby using compounds of types (a) and (b) together in a co-polymer ofpolystyrene compared with Examples J, K and L not containing compounds(a) and (b).

EXAMPLES 32 TO 44

The compositions shown in Tables 5, 6 and 7 were prepared by mixing thecomponents for 10-15 minutes at 240° C. followed by pressing for 10minutes at 240° C. to give a sheet of polystyrene/polyphenylene etherblend.

                                      Table 5                                     __________________________________________________________________________    Flame Retardant Tests in polystyrene/polyphenylene ether blend (Noryl         731-604)                                                                                                  Method                                                                        of    Parts             Other                                                                              Oxygen               Example                     Prep- of                Additive                                                                           Index                No.    R               X  n aration                                                                             compound I                                                                            Phosphorus ester                                                                        (Parts)                                                                            %                    __________________________________________________________________________    Compa-                                                                        rative                                                                        Example                                                                       M      --              -- --                                                                              --    --      --        --   22.3                 N      --              -- --                                                                              --    --      TPP(25)   --   28.1                 32                                                                                    ##STR17##      OH 2 D     10      TPP(25)   --   39.2                 33                                                                                    ##STR18##      OH 2 D     7.5     TPP(18.5) --   40.1                 __________________________________________________________________________

                                      table 6                                     __________________________________________________________________________    Flame Retardant Tests in polystyrene/polyphenylene ether blend (Noryl         110-780)                                                                                                  Method                                                                        of   Parts           Oxygen                       Example                     Prep-                                                                              of              Index                        No.   R             n X     aration                                                                            compound I                                                                           Phosphorus ester                                                                       %                            __________________________________________________________________________    Compara-                                                                      tive                                                                          Example                                                                       O     --            --                                                                              --    --   --     --       20.3                         Compara-                                                                      tive                                                                          Example                                                                       P     --            --                                                                              --    --   --     TPP (25) 27.1                         34                                                                                   ##STR19##    2 OCH.sub.3                                                                           B    11.3   TPP (25) 37.9                         35                                                                                   ##STR20##    2 OCOCH.sub.3                                                                         C    14     TPP (25) 39.7                         36                                                                                   ##STR21##    2 OH    D    10     TPP (25) 38.8                         37                                                                                   ##STR22##    2 OH    D    7.5      TPP (18.75)                                                                          42.3                         38                                                                                   ##STR23##    2 OH    D    4      TPP (10) 40.6                         39                                                                                   ##STR24##    2 OH    D    2      TPP (5)  35.9                         40                                                                                   ##STR25##    2 OH    D    8      TPP (10) 39.1                         Compara-                                                                      tive                                                                          Example                                                                       Q     --            --                                                                              --    --   --     TDBP (10)                                                                              26.7                         41                                                                                   ##STR26##    2 OH    D    5      TDBP (10)                                                                              28.1                         __________________________________________________________________________     TPP = Triphenyl phosphate                                                     TDBP = Tris(2,3-dibromopropyl)phosphate                                  

                                      Table 7                                     __________________________________________________________________________    Flame Retardant Tests in Polystyrene/Polyphenylene Ester Blend (Noryl SE1     211)                                                                                               Method                                                                        of   Parts        Oxygen                                 Example              Prep-                                                                              of     Phosphorus                                                                          Index                                  No.    R        n  X aration                                                                            compound I                                                                           ester %                                      __________________________________________________________________________    Compara-                                                                      tive                                                                          Example                                                                       R      --       -- --                                                                              --   --     --    29.3                                   Compara-                                                                      tive                                                                          Example                                                                       S      --       -- --                                                                              --   --     TPP (10)                                                                            36.3                                   42                                                                                    ##STR27##                                                                             OH 2 D    4      TPP (10)                                                                            39.4                                   43     "        OH 2 D    4      TPP (5)                                                                             41.5                                   44     "        OH 2 D    2      TPP (5)                                                                             37.3                                   __________________________________________________________________________     TPP = Triphenyl phosphate                                                

The results in Tables 5, 6 and 7 show the effect inpoly/styrene/polyphenylene ether of using combinations of (a) and (b).Marked improvement in flame retardancy is observed over comparativeexamples M, N, O, P, Q, R and S which contain no additive or onlycompound (a).

EXAMPLES 45 TO 67

Tables 8 and 9 show the flame retardant effect achieved when naphthaleneoligomers are used in conjunction with a phosphorus compound to flameretard polystyrene/polyphenylene ether and polystyrene respectively. Theresults show the marked improvement in using (a) and (b) compared withthe Examples T to W.

                                      Table 8                                     __________________________________________________________________________    Flame Retardant Tests in Polystyrene/Polyphenylene Ether Blend using          Oligomers                                                                                               Method                                                                             Phos-                                                                Parts                                                                             of   phorus       Oxygen                            Example           M.  Cpd.                                                                              prepar-                                                                            ester        Index                             No.    Compound I Wt. I   ation                                                                              (parts)                                                                            Polymer %                                 __________________________________________________________________________    45   Naphthalene Oligomer                                                                       550 4   E    TPP(10)                                                                            Noryl 110-780                                                                         36.0                              46   Naphthalene Oligomer                                                                       550 8   E    TPP(10)                                                                            "       39.4                              47   Naphthalene Oligomer                                                                       550 2   E    TPP(5)                                                                             "       32.0                              48   Naphthalene Oligomer                                                                       550 4   E    TPP(5)                                                                             "       33.4                              49   Oligomer prepared from                                                                     530 10  G    TPP(25)                                                                            "       43.7                                   mono and bis-hydroxy                                                          methyl naphthalene                                                       50   Oligomer prepared from                                                                     530 10       TPP(25)                                                                            "       50.1                                   4,4'-bis-hydroxy methyl                                                       biphenyl                                                                 51   Naphthalene oligomer                                                                       380 4   F    TPP(10)                                                                            "       36.0                              52   Naphthalene oligomer                                                                       380 8   F    TPP(10)                                                                            "       39.4                              53   Naphthalene oligomer                                                                       380 2   F    TPP(5)                                                                             "       32.0                              54   Naphthalene oligomer                                                                       380 4   F    TPP(5)                                                                             "       33.4                              55   Naphthalene oligomer                                                                       380 8   F    TPP(5)                                                                             "       35.2                              56   Naphthalene oligomer                                                                       380 4   F    TPP(10)                                                                            Noryl Se1-211                                                                         39.6                              57   Naphthalene oligomer                                                                       380 2   F    TPP(5)                                                                             "       36.5                              Compa-                                                                        rative                              NORYL 110-780                             Examples                                                                      T    --           --  --       TPP(S)                                                                             "       25.0                              U    --           --  --       TPP(10)                                                                            "       28.0                              V    --           --  --       TPP(25)                                                                            "       28.1                              __________________________________________________________________________     TPP-Triphenyl phosphate                                                  

                                      Table 9                                     __________________________________________________________________________    Flame Retardant Tests in Polystyrene using Oligomers                                                   Method                                                                    Parts                                                                             of   Phosphorus                                                                             Oxygen                                 Example          M.  Cpd.                                                                              prepar-                                                                            Ester    Index                                  No.  Compound I  Wt. I   ation                                                                              (parts)  %                                      __________________________________________________________________________    58   Naphthalene Oligomer                                                                      550  5  E    TPP (12.5)                                                                             24.0                                                                 TCEP (12.5)                                     59   "           550 10  E    TCEP (12.5)                                                                            35.2                                   60   "           550 15  E    TCEP (12.5)                                                                            41.9                                   61   "           550 20  E    TCEP (12.5)                                                                            57.0                                   62   "           550 23  E    TCEP (12.5)                                                                            58.5                                   63   "           550 10  E    TPP (20) 41.5                                                                 TCEP (5)                                        64   "           550 10  E    TPP (25) 33.3                                   65   "           550 10  E    TPP (12.5) +                                                                           33.1                                                                 bis (chloro-                                                                  ethyl)phenyl                                                                  phosphate (12.5)                                66   "           380 10  F    isopropylphenyl-                                                                       39.7                                                                 phenyl phosphate                                                              (Reofos 95) (25)                                67   "           380 10  F    diphenyl decyl                                                                         37.8                                                                 phosphate (25)                                  Compa-                                                                        rative                                                                        Example                                                                       W    --          --  --       TPP (20) +                                                                             23.0                                                                 TCEP (5)                                        __________________________________________________________________________     TPP = Triphenyl phosphate                                                     TCEP = Tris(chloroethyl)phosphate                                        

EXAMPLES 68 TO 70

The composition shown in Table 10 were prepared by mixing the componentsfor 10-15 minutes at 250° C. followed by pressing for 10 minutes at 240°C. to give a sheet of polycarbonate.

The results in Table 10 show the marked improvement in flame retardancyby using compounds of type (a) and (b) together in polycarbonatecompared with the comparative Examples A¹, B¹, C¹ and D¹ not containingcompounds (a) plus (b).

EXAMPLES 71 AND 72

The compositions shown in Table 11 were prepared by mixing thecomponents at 270°-280° C. for 10-15 minutes followed by pressing for 10minutes at 250° C. to give a sheet of polyphenylene oxide.

The results in Table 11 show the marked improvement in flame retardancyby using compounds of type (a) and (b) together in polyphenylene oxidecompared with the Examples E¹, F¹ and G¹ not containing compounds (a)plus (b).

EXAMPLES 73-79

The compositions shown in Table 12 were prepared by the same procedureas Examples 68 and 69.

The results in Table 12 show the marked improvement in flame retardancyby using compounds of type (a) and (b) together in polycarbonatecompared with the Examples H¹, I¹, J¹, K¹, L¹ and M¹ not containingcompounds (a) plus (b).

                                      Table 10                                    __________________________________________________________________________    Flame Retardant Tests in Polycarbonate (Lexan 141)                                                        Method                                                                        of   Parts            Oxygen                      Example                     Prep-                                                                              of               Index                       No.   R               n X   aration                                                                            compound I                                                                           Phosphorus ester                                                                        %                           __________________________________________________________________________    Compara-                                                                      tive                                                                          Example                                                                       A.sup.1                                                                             --              --                                                                              --  --   --     --        26.3                        B.sup.1                                                                             --              --                                                                              --  --   --     TPP(10)   32.5                        68                                                                                   ##STR28##      2 OH  D    4      TPP(10)   49.5                        69                                                                                   ##STR29##      2 OCH.sub.3                                                                         B    4      TPP(10)   37.5                        C.sup.1                                                                             --              --                                                                              --  --   --     --        26.8                        D.sup.1                                                                             --              --                                                                              --  --   --     TPP(5)    28.3                        70                                                                                   ##STR30##      2 OH  D    4      "         34.0                        __________________________________________________________________________     TPP =  Triphenyl phosphate                                               

                                      Table 11                                    __________________________________________________________________________    Polyphenylene Oxide                                                                                      Method                                                                        of   Parts            Oxygen                       Example                    Prep-                                                                              of               Index                        No.   R               n X  aration                                                                            compound I                                                                           Phosphorus ester                                                                        %                            __________________________________________________________________________    Compara-                                                                      tive                                                                          Example                                                                       E.sup.1                                                                             --              --                                                                              -- --   --     --        29.4                         F.sup.1                                                                             --              --                                                                              -- --   --     TDBP(10)  31.8                         G.sup.1                                                                             --              --                                                                              -- --   --     TDBP(25)  37.5                         71                                                                                   ##STR31##      2 OH D    4      TDBP(10)  33.5                         72    "               2 OH D    10     TDBP(25)  45.0                         __________________________________________________________________________     TDBP = Tris(2,3-Dibromopropyl)phosphate                                  

                                      Table 12                                    __________________________________________________________________________    Flame Retardant Tests in Polycarbonate (Lexan 141)                            using Naphthalene Oligomers.                                                                          Method                                                                             Phos-                                                                 Parts                                                                            of   phorus                                                                              Oxygen                                     Example           M. Cpd.                                                                             prepar-                                                                            ester Index                                      No.   Compound I  Wt.                                                                              I  ation                                                                              (parts)                                                                             %                                          __________________________________________________________________________     73   Naphthalene Oligomer                                                                      540                                                                              4  E    TPP(5)                                                                              30.4                                       74    "           540                                                                              5  E    TCEP(5)                                                                             50.5                                                                    TPP(20)                                          75    "           440                                                                              10 E    TPP(25)                                                                             51.5                                       76    "           440                                                                              4  E    TPP(10)                                                                             39.4                                       Compara-                                                                      tive                                                                          Example                                                                       H.sup.1                                                                             --          -- --      TPP(25)                                                                             36.0                                       I.sup.1                                                                             --          -- --      TPP(10)                                                                             32.5                                       J.sup.1                                                                             --          -- --      TPP(5)                                                                              28.3                                       K.sup.1                                                                             --          -- --      TCEP(5)                                                                             37.5                                                                    TPP(20)                                          L.sup.1                                                                             --          -- -- --   --    26.3                                       M.sup.1                                                                             --          -- -- --   Triphenyl                                                                     phosphate(5)                                                                        28.3                                       77    Naphthalene Oligomer                                                                      380                                                                              4  F    "     30.4                                       78    "           380                                                                              6  F    "     38.4                                       79    "           380                                                                              8  F    "     38.3                                       __________________________________________________________________________     TCEP = Tris(2-chloroethyl)Phosphate                                           TPP = Tri-phenyl Phosphate                                               

EXAMPLES 80 TO 107

The used polyester A is a 70% solution in styrene of a polyester madefrom dipropylene glycol (2.2 mol), phthalic anhydride (0.5 mol), adipicacid (0.5 mol), and maleic anhydride (1 mol).

The compositions shown in Tables 13 to 17 were prepared by mixing thepolyester solution and the flame retarders, then adding 2 p.h.r. (basedon the resin) of 50% methyl ethyl ketone peroxide (MEKP) catalyst. Themixture was poured into a 2.5×4.0×0.1 inch (63×100×2,5 mm) tray, apolyester film laid across the surface to exlude air, and cured at 60°for 20-24 hours. On removal from the tray, the resulting "tile" was thencut to 0.25"×0.100"×3" (6×76×2,5 mm), the size required for testing.

The results in Tables 13 to 17 show the effect in styrene curedpolyester resin of using combinations of (a) and (b). Marked improvementin flame retardancy is observed over the comparative examples whichcontain no additive or only compound (a).

                                      Table 13                                    __________________________________________________________________________    Flame Retardant Tests in Styrene Cured Polyester Resin A                                                 Method                                                                        of   Parts              Oxygen                     Example                    Prep-                                                                              of     Phosphorus ester                                                                          Index                      No.   R               n X  aration                                                                            compound I                                                                             (Parts)   %                          __________________________________________________________________________    Compara-                                                                      tive                                                                          Example                                                                       N.sup.1                                                                             --              --                                                                              -- --   --       --        18.2                       O.sup.1                                                                             --              --                                                                              -- --   --     Tris(2,3-dibromo-                                                                         21.6                                                              propyl)phosphate                                                              (25)                                   P.sup.1                                                                             --              --                                                                              -- --   --     Tris(2-chloro-                                                                            24.2                                                              ethyl)phosphate                                                               (25)                                   Q.sup.1                                                                             --              --                                                                              -- --   --     Trioctyl phosphate                                                                        20.2                                                              (25)                                   R.sup.1                                                                             --              --                                                                              -- --   --     Octyl diphenyl                                                                            19.9                                                              phosphate(25)                          80                                                                                   ##STR32##      2 OH D    10     Tris(2,3-dibromo-  propyl)phosphate                                             (25)      39.3                       81                                                                                   ##STR33##      2 OH D    10     Tris(2-chloro-  ethyl)phosphate(25)                                           4           40.8                       82                                                                                   ##STR34##      2 OH D    10     Trioctyl phosphate  (25)                                                                  30.3                       83                                                                                   ##STR35##      2 OH D    10     Octyl diphenyl  phosphate(25)                                                             22.9                       __________________________________________________________________________

                                      Table 14                                    __________________________________________________________________________    Flame Retardant Test in Styrene Cured Polyester Resin A                                              Method                                                                        of   Parts             Oxygen                          Example       Molecular                                                                              Prep-                                                                              of     Phosphorus ester                                                                         Index                           No.   Compound I                                                                            Weight   aration                                                                            compound I                                                                           (Parts)    %                               __________________________________________________________________________    84    Naphthalene                                                                           550      E    10     Tris(2-chloro-                                                                           39.2                                  oligomer                     ethyl)phosphate                                                               (25)                                       85    Naphthalene                                                                           380      F    10     Tris(2-chloro-                                                                           41.5                                  oligomer                     ethyl)phosphate                                                               (25)                                       Compara-                                                                      tive                                                                          Example                                                                       S.sup.1                                                                               --    --            --     Tris(2-chloro-                                                                           24.2                                                               ethyl)phosphate                                                               (25)                                       86    Naphthalene      E    4      Tris(2-chloro-                                                                           25.4                                  oligomer                     ethyl)phosphate                                                               (5)                                        Compara-                                                                      tive                                                                          Example                                                                       T.sup.1                                                                             ° --                                                                           --       --   --     Tris(2-chloro-                                                                           21.6                                                               ethyl)phosphate                                                               (5)                                        87    Naphthalene                                                                           530      G    10     Tris(2-chloro-                                                                           35.0                                  oligomer                     ethyl)phosphate                                                               (25)                                       Compara-                                                                      tive                                                                          Example                                                                       V.sup.1                                                                             --      --       --   --     Tris(2-chloro-                                                                           24.2                                                               ethyl)phosphate                                                               (25)                                       88    Naphthalene                                                                           530      G    10     Diphenyl ethyl                                                                           33.3                                  oligomer                     phosphate (25)                             Compara-                                                                      tive                                                                          Example                                                                       V.sup.1                                                                             --      --       --   --     --         23.0                            __________________________________________________________________________

                                      Table 15                                    __________________________________________________________________________    Flame Retardant Test in Styrene Cured Polyester Resin A                       __________________________________________________________________________                               Method                                                                             Parts                                                                    of   of                        Oxygen              Example                    prep-                                                                              Com- Phosphorus Ester     Index               No.   Compound I    X  n   aration                                                                            pound I                                                                            (parts)              %                   __________________________________________________________________________    89                                                                                   ##STR36##    OH 2   D     4   Tris-(2-chloroethyl) phosphate                                                                     24.5                Compara-                                                                      tive                                                                          Example                                                                       W.sup.1                                                                             --            -- --  --   --   Tris-(2-chloroethyl) 21.6                                                     phosphate (5)                            90                                                                                   ##STR37##    OH 2   D    10   Diphenyl 2-trichloro- ethyl                                                   phosphate (25)       31.0                Compara-                                                                      tive                                                                          Example                                                                       X.sup.1                                                                             --            -- --  --   --   Diphenyl 2-trichloro-                                                                              23.0                                                     ethyl phosphate (25)                     91                                                                                   ##STR38##    OH 2   D    10                                                                                  ##STR39##           26.4                Compara-                                                                      tive                                                                          Example                                                                       Y.sup.1                                                                             --            -- --  --   --     "                  22.8                __________________________________________________________________________                               Method                                                                             Parts                                                                    of   of                        Oxygen              Example                    Prep-                                                                              com- Phosphorus ester     Index               No.   Compound I    n  X   aration                                                                            pound I                                                                            (Parts)              %                   __________________________________________________________________________    92                                                                                   ##STR40##    2  OCH.sub.3                                                                         B    10   Triphenyl phos- phate                                                                              27.6                Compara-                                                                      tive                                                                          Example                                                                       Z.sup.1                                                                             --            -- --  --   --   Triphenyl phos-      21.4                                                     phate (25)                               93                                                                                   ##STR41##    2  OH  D    10   Triphenyl phos- phate                                                                              32.0                94                                                                                   ##STR42##    2  OCH.sub.3                                                                         B    10   Tris(2-chloro- ethyl)phosphate                                                                     33.8                95                                                                                   ##STR43##    2  Cl  A    10   Tris(2-chloro- ethyl)phosphate                                                                     26.3                96                                                                                   ##STR44##    2  OH  D    10   Tris(2-chloro- ethyl)phosphate                                                                     31.2                97                                                                                   ##STR45##    2  OH  D    10   Tri-allyl phos- phate                                                                              23.6                Compara-                                                                      tive                                                                          Example                                                                       A.sup.2             -- --       --   Tri-allyl phos-      20.6                                                     phate (25)                               98                                                                                   ##STR46##    2  OH  D     5   Tris(2,3-dibromo- propyl phosphate                                            (10)                 28.5                99    "             2  OH  D    10   Tris(2-chloro-       26.6                                                     ethyl) (5)                               100   "             2  OH  D     2   Tris(2-chloro-       33.3                                                     ethyl) (13)                              101   "             2  OH  D    7.5  Tris(2-chloro-       28.4                                                     ethyl) (7.5)                             102                                                                                  ##STR47##    2  OH  D     5   Tris(2-chloro- ethyl)                                                                              31.9                Compara-                                                                      tive                                                                          Example                                                                       B.sup.2                                                                             --            -- --  --   --   Tris(2-chloro-       21.6                                                     ethyl) (5)                               C.sup.2                                                                             --            -- --  --   --   Tris(2-chloro-       22.4                                                     ethyl) (10)                              D.sup.2                                                                             --            -- --  --   --   Tris(2-chloro-       23.0                                                     ethyl) (15)                              __________________________________________________________________________

                                      Table 16                                    __________________________________________________________________________    Flame Retardant Tests in Styrene Cured Poleyster Resin A                      using a supplementary additive                                                                        Method                                                                             Parts                                                                    of   of   Phosphorus              Oxygen              Example                 prep-                                                                              Com- Ester  Additive         Index               No.  R             X  n aration                                                                            pound I                                                                            (parts)                                                                              (parts)          %                   __________________________________________________________________________    103                                                                                 ##STR48##    OH 2 D    5    Tris(2-chloro- ethyl)phos- phate                                                      ##STR49##       28.8                104                                                                                 ##STR50##    OH 2 D    5    Tris(2 -chloro- ethyl)phos- phate                                                     ##STR51##       37.7                __________________________________________________________________________

                                      table 17                                    __________________________________________________________________________    Flame Retardant Tests in Styrene Cured Polyester Resin A using                PVC as a filler                                                                                     Method                                                                             Parts                                                                    of   of   Phosphorus       Oxygen                       Example               prep-                                                                              Com-  Ester PVC Stabiliser                                                                          Index                        No.  R           X  n aration                                                                            pound I                                                                             (parts)                                                                             (parts)                                                                            (parts)                                                                            %                            __________________________________________________________________________    105                                                                                 ##STR52##  OH 2 D    10   Tris(2,3- dibromo- propyl) phosphate                                                 105)                                                                               Epoxidised  Soya Bean   Oil                                                  (2)   32.0                         106  "           OH 2 D    10   Tris(2,3-                                                                            30    "   34.0                                                         dibromo-                                                                      propyl)                                                                       phosphate                                                                     (25)                                          107  "           OH 2 D    10   Tris(2,3-                                                                            10    --  31.8                                                         dibromo-                                                                      propyl)                                                                       phosphate                                                                     (25)                                          __________________________________________________________________________

EXAMPLES 108 TO 120

The following polyesters or esters were used:

Polyester B

denotes a 70% solution in styrene of a polyester made from propyleneglycol (3.15 mol), phthalic anhydride (2 mol), and maleic anhydride (1mol).

Ester C

denotes a 70% solution in styrene of2,2-bis(4-(3-methacryloxy-2-hydroxypropoxy phenyl)propane.

Polyester D

denotes a 70% solution in styrene of a polyester made from dipropyleneglycol (2.2 mol), adipic acid (0.5 mol),1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-ene 2,3-dicarboxylic acidanhydride (0.5 mol) and maleic anhydride (1 mol).

Polyester E

denotes a commercially available solution in styrene of an unsaturatedpolyester resin based on a 2,2-bis(4-(hydroxyalkoxy)phenyl)-propane.

Ester F

denotes a 70% solution in 1,1,1-trimethylolpropane trimethacrylate of2,2-bis(4-(3-methacryloxy-2-hydroxy-propoxy)phenyl)propane.

Ester G

denotes an 83.3% solution in diallyl phthalate of2,2-bis(4-(3-methacryloxy-2-hydroxypropoxy)phenyl)propane.

The parts of (a) and (b) indicated in table 18 were mixed with 100 partsof the polyester solutions. Then the indicated parts of a siccativecontaining 8% cobalt and of the curing catalyst (a 60% dispersion ofethyl methyl ketone peroxide in dimethyl phthalate) were added. Themixtures were poured into a try as in examples 80-107, the curinghowever was carried out by steps.

Firstly the casting was allowed to gel overnight at room temperature,followed by heating for 1 hour to 50° C. and 1 hour to 80° C.

                                      Table 18                                    __________________________________________________________________________    Flame Retardant Tests in a Series of Polyester Resins                                                              Parts                                                                    Method                                                                             of  Phos-             Oxy-                                               of   Com-                                                                              phorus                                                                              Sicc-                                                                             Cat-                                                                              Poly-                                                                             gen                Example                         Prep-                                                                              pound                                                                             Compound                                                                            active                                                                            alyst                                                                             ester/                                                                            Index              No.  R                    X   n aration                                                                            I   (parts)                                                                             (parts)                                                                           (parts)                                                                           Ester                                                                             %                  __________________________________________________________________________    Compar-                                                                            --                   --  --                                                                              --   --  Triphenyl                                                                           0.5 4   B   20.5               ative                                    phosphate                            Example                                  (20)                                 E.sup.2                                                                       108                                                                                 ##STR53##           OH  2 D    10  Triphenyl phosphate (20)                                                            0.5 "   B   24.5               Compar-                                                                       ative                                                                         Example                                                                       F.sup.2                                                                            --                   --  --                                                                              --   --  Triphenyl                                                                           0.125                                                                             "   C   20                                                          phosphate                                                                     (20)                                 109                                                                                 ##STR54##           OH  2 D    10  Triphenyl phosphate (20)                                                            0.125                                                                             "   C   29.5               Compar-                                                                       ative                                                                         Example                                                                       G.sup.2                                                                            --                   --  --                                                                              --   --  Triphenyl                                                                           0.5 "   D   22.5                                                        phosphate                                                                     (20)                                 110                                                                                 ##STR55##           OH  2 D    10  Triphenyl phosphate (20)                                                            0.5 "   D   24.0               111                                                                                 ##STR56##           OCH.sub.3                                                                         2 C    10  Triphenyl phosphate (20)                                                            0.5 "   D   26.5               112                                                                                 ##STR57##           OH  2      10  Triphenyl phosphate (20)                                                            0.5 "   D   30.0               Compar-                                  Triphenyl                            ative                                                                              --                   --  --                                                                              --   --  phosphate                                                                           0.5 4   E   22.8               Example                                  (20)                                 H.sup.2                                                                       113                                                                                 ##STR58##           OCH.sub.3                                                                         2 B    10  Triphenyl phosphate (20)                                                            0.5 "   E   24.1               Compar-                                                                       ative                                                                         Example                                                                       K.sup.2                                                                            --                   --  --                                                                              --   --  20    0.5 "   F   23.5               114                                                                                 ##STR59##           OCH.sub.3                                                                         2 B    10  "     0.5 "   F   31.5               115                                                                                 ##STR60##           OH  2 D    10  "     0.5 "   F   32.5               116                                                                                 ##STR61##           OH  2      10  "     0.5 "   F   31.0               Compar-                                                                       ative                                                                         Example                                                                       L.sup.2                                                                            --                   --  --                                                                              --   --  "     0.5 "   G   20.5               117                                                                                 ##STR62##           OCH.sub.3                                                                         2 B    10  20    0.5 4   G   29.0               118                                                                                 ##STR63##           OH  2 D    10  Triphenyl Phosphine Oxide                                                           0.5)                                                                              4   B   21.3               Compar-                                                                       ative                                                                         Example                                                                       M.sup.2                                                                            --                   --  --                                                                              --   --  Triphenyl                                                                           "   "   B   18.5                                                        Phosphine                                                                     Oxide (20)                           119                       OH  2 D    10  Diamm-                                                                              "   "   B   21.0                                                        onium                                                                         hydrogen                                                                      phosphate                                                                     (20)                                 Compar-                                                                       ative                                                                              --                   --  --                                                                              --   --  Diamm-                                                                              "   "   B   16.4               Example                                  onium                                N.sup.2                                  hydrogen                                                                      phosphate                                                                     (20)                                 __________________________________________________________________________

What we claim is:
 1. A composition which comprises a polymer selectedfrom the group consisting of(1) a homopolymer or copolymer of styrene orα-methyl styrene, (2) a blend of (1) with polyphenylene oxide,polysulfone, vinyl chloride resin or polycarbonate, (3) a styrene curedunsaturated polyester resin, and (4) a polymer containing an aromaticgroup in the polymer chain and selected from the group consisting ofpolycarbonates, polyphenylene ethers, polysulfides, polyurethanes,polyhydrazides, linear polyesters, polysulfones, polyamides,polyimides,polybenzimidazoles and polyanhydrides,and a flame-retarding combinationof (a) a phosphorus compound selected from the group consisting of aphosphine oxide, a phosphorus oxy acid, a salt of a phosphorus oxy acidand an ester of a phosphorus oxy acid, and (b) a compound of the formula

    (A).sub.a (--CH.sub.2 --).sub.b [--CH.sub.2 (OCH.sub.2).sub.m OCH.sub.2 --].sub.c (--CH.sub.2 OH).sub.d

whereinA is an unsubstituted aromatic hydrocarbon, an aromatichydrocarbon substituted by up to two substituents selected from thegroup of halogen, alkyl with 1 to 4 cabon atoms, haloalkyl with 2 to 4carbon atoms, hydroxyl, alkoxy with 1 to 4 carbon atoms or acyloxy with2 to 4 carbon atoms, or diphenyl ether radical, a is 2 to 20 and isequal to b+c+1, b is 0 to 19, c is 0 to 19, d is 0 to 2a, and m is 0 to10,there being present per molecule (a) at least two of the groups (CH₂OH), (b) at least two of the groups (--CH₂ OCH₂ --) or (c) at least onegroup (CH₂ OH) and one group (--CH₂ OCH₂ --) and wherein the groups(--CH₂ --), [--CH₂ (OCH₂)_(m) OCH₂ --] and (--CH₂ OH) are all directlyattached to the nucleus of radicals A only.
 2. A composition accordingto claim 1 wherein component (a) is an ester of a phosphorus oxy acid.3. A composition according to claim 1 wherein the amount of component(a) plus component (b) is from 1 to 100 parts by weight per 100 parts ofpolymer.
 4. A composition according to claim 3 wherein the amount ofcomponent (a) plus component (b) is from 2 to 35 parts by weight per 100parts of polymer.
 5. A composition according to claim 1 wherein theratio of component (a) to component (b) is from 1:10 to 10:1 by weight.6. A composition according to claim 5 wherein the ratio is from 1:1 to8:1.
 7. A composition according to claim 5 wherein the ratio is from 2:1to 4:1 by weight.
 8. A composition according to claim 1 wherein thepolymer is a homopolymer or copolymer of styrene or α-methyl styrene. 9.A composition according to claim 1 wherein the polymer is a copolymer ofstyrene with butadiene or butadiene/acrylonitrile.
 10. A compositionaccording to claim 1 wherein the polymer is a copolymer of styrene andan unsaturated polyester.
 11. A composition according to claim 1 whereinthe component (a) is an ester derived from phosphoric acid, phosphorusacid, a phosphonic acid, or a phosphinic acid.
 12. A compositionaccording to claim 11 wherein component (a) is an ester of an acidcontaining pentavalent phosphorus.
 13. A composition according to claim11 wherein the ester is a triaryl phosphate or tri-haloalkyl phosphate.14. A composition according to claim 1 wherein component (a) is aphosphine oxide.
 15. A composition according to claim 14 whereincomponent (a) is a triaryl phosphone oxide.
 16. A composition accordingto claim 1 wherein component (a) is a salt of a phosphorus acid.
 17. Acomposition according to claim 16 wherein component (a) is an alkalimetal, ammonium or amine salt of phosphoric acid, phosphorus acid, aphosphonic or a phosphonic acid.
 18. A composition according to claim 1wherein m is
 0. 19. A composition according to claim 1 wherein A is abenzene, naphthalene, anthracene, biphenyl or diphenyl ether radical.20. A composition according to claim 1 wherein A is unsubstituted or issubstituted by one of the substituents halogen, alkyl with 1 to 4 carbonatoms, haloalkyl with 2 to 4 carbon atoms, hydroxyl, alkoxy with 1 to 4carbon atoms or acyloxy with 2 to 4 carbon atoms.
 21. A compositionaccording to claim 1 wherein more than 50 mol % of residue A are derivedfrom naphthalene.
 22. A composition according to claim 21 wherein morethan 75 mol % of radicals A are derived from napthalene.
 23. Acomposition according to claim 1 wherein the oligomer (b) has a numberaverage molecular weight of from 300 to
 3500. 24. A compositionaccording to claim 23 wherein the average molecular weight is from 350to
 1500. 25. A composition according to claim 24 wherein the averagemolecular weight is from 400 to
 1000. 26. A composition according toclaim 1 wherein A is derived from naphthalene, the radicals being linkedby (--CH₂ OCH₂ --) groups in the positions 1,4; 1,5; 1,6; 1,7; 2,5; 2,6or 2,7 on the naphthalene radical.
 27. A composition according to claim26 wherein the radicals are linked in the 1,4 or 1,5 positions on thenaphthalene radical.
 28. A composition according to claim 1 additionallycontaining a heat stabilizer, light stabilizer, UV absorber,antioxidant, filler, pigment, lubricant, blowing agent, fungicide,additive to improve mould release, optical brightening agent or otherfire retardant additive.
 29. A composition according to claim 1 whereincomponent (b) is a compound of the formula ##STR64##